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Control of petroleum-hydrocarbon contaminated groundwater by intrinsic

and enhanced bioremediation

Article  in  Journal of Environmental Sciences · June 2010

DOI: 10.1016/S1001-0742(09)60190-X · Source: PubMed

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 Journal of Environmental Sciences 2010, 22(6) 864–871

Control of petroleum-hydrocarbon contaminated groundwater by intrinsic

and enhanced bioremediation
Ku-Fan Chen1 , Chih-Ming Kao2,∗, Chiu-Wen Chen3 , Rao Y. Surampalli4 , Mu-Sheng Lee5

1. Department of Civil Engineering, “National” Chi Nan University, Taiwan, China

2. Institute of Environmental Engineering, “National” Sun Yat-Sen University, Taiwan, China. E-mail: jkao@mail.nsysu.edu.tw
3. Department of Marine Environmental Engineering, “National” Kaohsiung Marine University, Taiwan, China
4. U.S. Environmental Protection Agency, Kansas City, Kansas, USA
5. Environmental Protection Bureau, Kaohsiung City Government, Taiwan, China

Received 02 October 2009; revised 18 December 2009; accepted 24 December 2009

Abstract
In the first phase of this study, the effectiveness of intrinsic bioremediation on the containment of petroleum hydrocarbons was
evaluated at a gasoline spill site. Evidences of the occurrence of intrinsic bioremediation within the BTEX (benzene, toluene,
ethylbenzene, and xylenes) plume included (1) decreased BTEX concentrations; (2) depletion of dissolved oxygen (DO), nitrate,
and sulfate; (3) production of dissolved ferrous iron, methane, and CO2 ; (4) deceased pH and redox potential; and (5) increased
methanogens, total heterotrophs, and total anaerobes, especially within the highly contaminated areas. In the second phase of this study,
enhanced aerobic bioremediation process was applied at site to enhance the BTEX decay rates. Air was injected into the subsurface
near the mid-plume area to biostimulate the naturally occurring microorganisms for BTEX biodegradation. Field results showed that
enhanced bioremediation process caused the change of BTEX removal mechanisms from anaerobic biodegradation inside the plume
to aerobic biodegradation. This variation could be confirmed by the following field observations inside the plume due to the enhanced
aerobic bioremediation process: (1) increased in DO, CO2 , redox potential, nitrate, and sulfate, (2) decreased in dissolved ferrous iron,
sulfide, and methane, (3) increased total heterotrophs and decreased total anaerobes. Field results also showed that the percentage
of total BTEX removal increased from 92% to 99%, and the calculated total BTEX first-order natural attenuation rates increased
from 0.0092% to 0.0188% per day, respectively, after the application of enhanced bioremediation system from the spill area to the
downgradient area (located approximately 300 m from the source area).

Key words: petroleum hydrocarbon; groundwater; natural attenuation; intrinsic bioremediation

DOI: 10.1016/S1001-0742(09)60190-X

Introduction to remove pollutants in the subsurface. Among those natu-

ral occurring processes, intrinsic bioremediation or natural
Releases of petroleum products (e.g., gasoline, diesel, bioremediation is one of the most important processes for
fuel oil) from above ground and underground storage contaminant removal (Sutherland et al., 2004; Chen et al.,
tanks or transport pipelines are the major causes of the 2006; Maier et al., 2007). The contaminants (e.g., BTEX)
groundwater pollution. Benzene, toluene, ethylbenzene, can be biodegradable under both aerobic and anaerobic
and xylene isomers (BTEX), the major components of conditions. Moreover, the aerobic degradation rates for
petroleum products, are toxic chemicals. The slow disso- BTEX are higher than those under anaerobic conditions
lution of residual BTEX from the spill location or source (Atteia and Guillot, 2007). The biodegradation processes
area usually causes in a BTEX plume in the subsurface. To are believed to be the major mechanisms that cause the
protect the subsurface receptors including drinking water reduction of the contaminant concentrations.
wells, the plume control action must be taken and operated Among commonly used groundwater remediation meth-
for a long period of time. ods, bioremediation is a more cost-effective technology
The field investigation results revealed that many of (Devlin et al., 2004; Sutherland et al., 2004; Chen et al.,
these subsurface contaminants naturally degrade before 2006; Neuhauser et al., 2009). Intrinsic bioremediation and
they reach a drinking water receptor (Brar et al., 2006; natural bioremediation have been considered as the po-
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Chen et al., 2006; Lai et al., 2007; Fraser et al., 2008). tential methods for the cleanup of petroleum-hydrocarbon
Monitored natural attenuation (MNA) is an in situ and in- contaminated sites. Because the intrinsic bioremediation
c.

active treatment system using natural occurring processes rate is limited by in situ environmental factors, enhanced in
situ bioremediation can be applied to stimulate pollutants
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* Corresponding author. E-mail: jkao@mail.nsysu.edu.tw

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No. 6 Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation 865

biodegradation. Moreover, microbiological investigations

of aquifer sediments have revealed the presence of mi-
crobial communities capable of degrading a broad range
of naturally occurring and xenobiotic compounds under a
broad range of environmental conditions (Kao et al., 2003,
2005). Thus, in situ aerobic bioremediation is a feasible
technology to cleanup BTEX contaminated sites if aquifer
oxygen can be supplied into the aquifer economically.
Enhanced aerobic bioremediation, such as injecting air
at a low rate into the aquifer below the zone of con-
tamination, is an effective mechanism for the removal
of petroleum hydrocarbons including BTEX (Wu et al.,
2005; Brar et al., 2006; Abu, 2008). At a relatively close
well spacing, the injected air promotes oxygenation of the
aquifer and thus promotes aerobic biodegradation (Ling
and Rifai, 2007; Balcke et al., 2009). In this study, the
enhanced aerobic bioremediation system is located to Fig. 1 Site map showing the groundwater flow direction, estimated
plume boundary, and soil and groundwater sampling locations.
focus upon BTEX for the purpose of stimulating aerobic
biodegradation of contaminants. In this study, a petroleum-
hydrocarbon spill site was selected to fulfill the following of this study, the effectivenesses of MNA and intrinsic
objectives: (1) to assess the occurrence and mechanisms of bioremediation on the containment of petroleum hydro-
intrinsic bioremediation, (2) to calculate the BTEX field- carbons was evaluated. In the second part of this study,
scale decay rates; and (3) to evaluate the effectiveness of enhanced BTEX decay rates and evidences of enhanced
enhanced aerobic bioremediation as a method for BTEX BTEX biodegradation through the enhanced aerobic biore-
control. mediation process were evaluated.

1 Study site 2 Materials and methods

A government owned tank farm facility site located For simplicity and ease of identification, the studied
in southern Taiwan was selected for this MNA study. In site was divided into five different areas (1 to 5), which
early 2000, leakage from a fuel-oil pipeline resulted in the represented the highly contaminated area (Area 1), mid-
groundwater contamination by petroleum hydrocarbons plume area (Area 2), downgradient area (Area 3), plume
(mainly BTEX). During the following four-year investi- edge area (Area 4), and background area (Area 5), respec-
gation period, more than 100 soil gas and soil samples tively. Five monitor wells, which were labeled as MW1,
were collected, and 18 monitor wells were installed for MW2, MW3, MW4, and MW5 were located inside the five
the site characterization and contaminated-groundwater representative areas (Areas 1 to 5) and used for ground-
extraction. On-site borings encountered up to 25 m of water sampling and analysis. All wells were screened
mostly brown to gray, fine to medium sand to silty sand. from 2 to 5.1 m below land surface (bls). Groundwater
The average groundwater elevation within the shallow samples were collected quarterly and analyzed for organic
aquifer is approximately 1.5 to 2.5 m below land surface. compounds and geochemical indicators including BTEX,
Groundwater in the unconfined aquifer, according to the CH4 , CO2 , inorganic nutrients, anions, Fe(II), pH, redox
groundwater elevation in site monitor wells, flows south- potential (Eh), and DO during the two-year investiga-
west. The measured effective porosity is 0.27, and the tion period (first part of this study). Organic compound
average hydraulic conductivity for the surficial, unconfined analyses were performed in accordance with U.S. EPA
aquifer is 1.15 × 10−3 m/sec (99 m/day). The calculated Method 602, using a Tekmer Purge-and-Trap Model LSC
site groundwater flow velocity is 1.32 × 10−5 m/sec (1.14 2000 with a Perkin-Elmer Model 9000 Auto System
m/day). The measured groundwater temperature in the Gas Chromatograph (GC). Methane was analyzed on a
surficial aquifer varies from 17 to 29°C. The preliminary Shimadzu GC-9A GC using headspace techniques. Ion
site investigation results indicated that the BTEX plume chromatography (Dionex) was used for inorganic nutrients
is approximately 480 m in length (along the groundwater and anions (NO3 − , SO3 2− , SO4 2− ) analyses. Sulfide was
flow direction) and 220 m in width (data not shown). analyzed by Methylene-Blue method (APHA, 2001) using
Figure 1 presents the site map showing the estimated Hach technique (Hach Co., USA). Perkin-Elmer Plasma
plume boundary, locations of representative monitor wells II Inductively Coupled Plasma-Argon Emission Spectrom-
and soil sampling, and groundwater flow direction. eter (ICP-AES) was used for Fe(II) analyses following
Since 2005, MNA has been applied to remediate Standard Methods (APHA, 2001). DO, Eh, pH, CO2 , and
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contaminated groundwater. In 2007, enhanced aerobic temperature were measured in the field. A pH/Eh meter
bioremediation system was installed in the mid-plume (Accumet 1003, Fisher Scientific, USA) was used for pH
c.

area to evaluate the effectiveness of enhanced aerobic and Eh measurement, a DO meter (Orion Model 840,
.a

bioremediation system on BTEX removal. In the first part Thermo Scientific, USA) was used for DO and temperature
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866 Ku-Fan Chen et al. Vol. 22

measurement, and a Hach digital titrator cartridge was used contaminant concentration at MW1; Kna (day−1 ) is the
for CO2 measurement. first-order decay rate (natural attenuation rate); t (day) is
To further confirm the occurrence of intrinsic bioreme- the ratio of distance between MW1 and MW2 (or MW3)/
diation and evaluate the trend of the degradation processes, groundwater flow velocity.
aquifer sediments were collected from the soil borings The enhanced aerobic bioremediation system consisted
SB1, SB2, SB3, SB4, and SB5, which were adjacent to of two air injection wells (injection points) (well screen
MW1, MW2, MW3, MW4, and MW5, respectively. Each at 4.7 to 5 m bls), air compressors, flow indicators,
soil core was analyzed for microbial enumeration to define inline regulators, and pressure gauges. The air flow was
the distribution of methanogens, total heterotrophs, and approximately 0.06 to 0.17 m3 /min (2 to 6 cfm) for each
total anaerobes. Total anaerobes and methanogens were air injection well. The four air injection wells were located
enumerated using a five-tube MPN assay. The total anaer- upgradient of MW2 (Fig. 1). Preliminary results indicated
obe tubes contained media described by Kao et al. (2001) that the radius of influence for the air injection well was
and were scored positive based on optical density. Total approximately 5.5 m (data not shown). All selected wells
plate counts were conducted using plate count agar (Difco) were sampled bimonthly during the eight-month investiga-
to assess the approximate size of the total heterotrophic tion period. Groundwater samples from the monitor wells
bacterial using the spread plate method (APHA, 2001). were collected and analyzed for organic compounds and
The methanogen tubes contained 20% H2 and 80% CO2 geochemical indicators described above.
in the headspace, and were scored positive based on the
production of methane (Kao et al., 2001). In this study, 3 Results and discussion
monitor wells (MW6, MW7, MW2, MW8, and MW9)
located in the cross-section line of MW6 to MW9 were Groundwater samples were collected from monitor
selected to compare to total BTEX flux through the cross wells MW1, MW2, MW3, MW4, and MW5. Table 1
section before and after the operation of enhanced aerobic shows the averaged results of eight groundwater sampling
bioremediation system. events during the two-year investigation period before en-
The first-order decay model (Eq. (1)) was applied to hanced aerobic bioremediation process. Figure 2 presents
estimate the natural attenuation rate between upgradient the variations in BTEX concentrations in monitor wells
well (MW1) and downgradient wells (MW2 and MW3) (MW1 to MW4) before the operation of the enhanced aero-
using the measured contaminant (BTEX) concentrations in bic bioremediation system along the groundwater transport
MW1 and MW2. direction. Table 2 shows the percentage of contaminant
removal for each compound between monitor wells (MW1
C2 = C1 e−Kna t (1)
to MW2 and MW1 to MW3) before enhanced aerobic
where, C2 (µg/L) is the measured contaminant concen- bioremediation process. Aquifer sediments collected from
tration at MW2 (or MW3); C1 (µg/L) is the measured soil borings S1 to S5 was used for microbial enumeration.

Table 1 Concentrations of BTEX and indicating parameters in monitor wells before the operation of enhanced aerobic bioremediation system

MW1 MW2 MW3 MW4 MW5

Location High Mid Down Edge BK

Distance from MW1 (m) 0 200 300 415 –
Benzene (µg/L) 743 269 102 15 BDL
Toluene (µg/L) 712 187 19 2 BDL
Ethylbenzene (µg/L) 419 141 36 6 BDL
m+p-Xylene (µg/L) 593 179 21 5 BDL
o-Xylene (µg/L) 371 131 46 11 BDL
Total BTEX (µg/L) 2838 907 224 39 BDL
DO (mg/L) 0 0.1 1.2 1.7 3.2
Nitrate (mg/L) 0.1 0.7 3.5 3.9 6.2
Total iron (mg/L) 14.3 4.6 0.5 0.7 0.9
Ferrous iron (mg/L) 15.5 7.2 0.2 0.2 0.1
Sulfate (mg/L) 3 9 12 14 18
Sulfide (µg/L) 14 11 3 2 2
Carbon dioxide (mg/L) 136 112 67 54 43
Methane (mg/L) 11 5.3 0.1 0.05 0.05
pH 6.6 6.7 6.8 6.9 7.0
Redox potential (mV) –159 –98 78 126 206
Ammonia nitrogen (mg/L) 1.9 2.2 2.8 2.9 3.1
Phosphate (mg/L) 1.1 0.9 1.3 1.4 1.9
Temperature (°C) 24.2 24.1 23.9 24.1 24.2
Methanogen (cells/g) 5.4 × 103 (SB1) 4.6 × 102 (SB2) BDL (SB3) BDL (SB4) BDL (SB5)
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Total heterotrophs (cells/g) 1.2 × 105 (SB1) 2.8 × 105 (SB2) 6.2 × 105 (SB3) 5.1 × 104 (SB4) 2.7 × 104 (SB5)
Total anaerobes (cells/g) 6.3 × 104 (SB1) 1.2 × 104 (SB2) 2.7 × 102 (SB3) 1.5 × 102 (SB4) 1.1 × 102 (SB5)
c.

High: sample collected from the highly contaminated area; Mid: sample collected from the mid-plume area; Down: sample collected at the downgradient
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area; Edge: sample collected from the edge of the plume; BK: sample collected at the background area.
–: not available; BDL: below detection limit; SB: microbial enumeration was performed using soil sediments.
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No. 6 Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation 867

Table 2 Percentage of contaminant removal for each compound between monitor wells before enhanced aerobic bioremediation process

Benzene (%) Toluene (%) Ethylbenzene (%) m+p-Xylene (%) o-Xylene (%) Total BTEX (%)

MW1–MW2 63.8 73.7 66.4 69.8 64.7 68.0

MW1–MW3 86.3 97.3 91.4 96.5 87.6 92.1

along the transport path via natural attenuation process.

Results indicate that 68% and 92.1% of the total BTEX
were removed from MW1 to MW2 and from MW1 to
MW3, respectively.
The observed bacterial populations are presented in
Table 1. Figure 3 shows the microbial enumeration anal-
yses for five soil samples before the operation of the
enhanced aerobic bioremediation system. Results show
that significant amount of methanogens (>102 cells/g soil),
total heterotrophs and total anaerobes (>104 cells/g soil)
were detected in SB1 and SB2 soil samples collected
from the highly and mid plume areas, respectively. This
Fig. 2 Variations in BTEX concentrations in monitor wells (MW1 indicates that an increased petroleum hydrocarbons con-
to MW4) before the operation of the enhanced aerobic bioremediation
centrations and reduced conditions caused an increase in
system along the groundwater transport direction.
methanogenic and anaerobic bacterial population. Howev-
Results of the bacterial population assessment are also er, only 2.7 × 102 and 1.5 × 102 cells of total anaerobes/g
shown in Table 1. Results show that BTEX concentrations soil were observed in SB3 and SB4, respectively. This
in the monitor wells reached a relatively stable condition, indicates that anaerobic bacteria were not the dominant
and no significant decrease or increase in BTEX con- microbial population under anaerobic conditions. Field
centrations was observed during the investigation period. results also indicate that the anaerobic biodegradation pat-
This indicates that the presence of residual hydrocarbons terns were the dominant intrinsic biodegradation processes
beneath the former spill location is possible. in the source and mid-plume areas.
The dissolved BTEX are being continuously released The calculated first-order decay rates (natural atten-
from residual fuel globules into the groundwater, causing uation rates) for BTEX between MW 1 to MW2 and
the stable BTEX concentrations in monitor wells within MW1 to MW3 are presented in Table 3. The total BTEX
the investigation period. Investigation results indicate the decay rate was 0.0092 day−1 from MW1 to MW3. Re-
occurrence of the anaerobic conditions within the plume. sults show that toluene was the most quickly degraded
Compared to MW1 and MW2, the downgradient and compound in BTEX (up to 0.0131 day−1 ), followed by
plume edge monitor wells (MW3 and MW4) contained m+p-xylene (0.0121 day−1 ), ethylbenzene (0.0089 day−1 ),
higher O2 concentrations (up to 1.2 mg/L). This indicates o-xylene (0.0076 day−1 ), and benzene (0.0072 day−1 )
that the downgradient or edge of the plume was under between MW1 to MW3 (Table 3). The observed decay
the oxidized stage and aerobic biodegradation was the rates for BTEX were similar to the rates obtained from
dominant biodegradation process in the area. The declines other investigations (US EPA, 2004; Chen et al., 2005).
in Eh and DO near the source area reflect the change This indicates that the natural attenuation mechanisms
from oxidizing to reducing conditions. The increased CH4 were under acceptable ranges, and caused the removal of
(up to 11 mg/L in MW1) and CO2 (up to 136 mg/L
in MW1) concentrations, and decreased pH (pH = 6.6
in MW1) (Table 1) in MW1 and MW2 suggest that the
methanogenesis was the dominant biodegradation process
within the most of contaminated zone. This indicates that
significant microbial activity and intrinsic bioremediation
occurred in this area.
The lower nitrate and sulfate concentrations within the
plume reveal that both nitrate and sulfate acted as electron
acceptors after the depletion of oxygen. High ferrous
concentrations were detected in MW1 (15.5 mg/L) and
MW2 (7.2 mg/L) (Table 1). This indicates that ferric iron
might also act as the electron acceptor around the source
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area. The decrease in BTEX concentrations from MW1

to MW4 suggests the occurrence of natural attenuation of
c.

BTEX. Table 2 presents the percentage of concentration Fig. 3 Microbial enumeration analyses for five soil samples before the
.a

drop for each compound through MW1 to MW2 or MW3 operation of the enhanced aerobic bioremediation system.
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868 Ku-Fan Chen et al. Vol. 22

Table 3 Calculated first-order natural attenuation rates for each compound between monitor wells before enhanced aerobic bioremediation process

Benzene (day−1 ) Toluene (day−1 ) Ethylbenzene (day−1 ) m+p-Xylene (day−1 ) o-Xylene (day−1 ) Total BTEX (day−1 )

MW1–MW2 0.0056 0.0074 0.0061 0.0067 0.0058 0.0063

MW1–MW3 0.0072 0.0131 0.0089 0.0121 0.0076 0.0092

BTEX at studied site.

In the second part of this study, air injection wells were
installed for air supplement to the groundwater. Table 4
shows the groundwater average results in MW1 to MW5 of
four groundwater sampling events during a eight-month in-
vestigation after enhanced aerobic bioremediation process.
Figure 4 presents the variations in BTEX concentrations
in monitor wells (MW1 to MW4) after the operation of
the enhanced aerobic bioremediation system along the
groundwater transport direction. The significant decrease
in BTEX concentrations was observed after the operation
of enhanced aerobic bioremediation, which mainly due to
the enhanced aerobic biodegradation. The part of BTEX Fig. 4 Variations in BTEX concentrations in monitor wells (MW1 to
MW4) after the operation of the enhanced aerobic bioremediation system
loss might be also due to the vaporization. Because the
along the groundwater transport direction.
measured soil gas results from nine soil gas sampling wells
were insignificant (< 68 ppm) (data not shown) before
and after the enhanced aerobic bioremediation process, were detected in SB1 and SB2 soil sample collected from
the amount of BTEX loss due to volatilization would be the contaminated areas. This indicates that the increased
insignificant. Table 5 shows the percentage of contaminant petroleum hydrocarbons concentrations caused an increase
removal for each compound between monitor wells after in bacterial population. Moreover, a decrease in total
the enhanced aerobic bioremediation process. Results in- anaerobes was observed in SB2 and SB3 soil samples.
dicate that 85% and 99% of the total BTEX was removed Results show that only 1.3 × 102 and 1.6 × 102 cells
from MW1 to MW2 and from MW1 to MW3, respectively. of total anaerobes/g soil were observed in SB2 and SB3,
Figure 5 shows the results of microbial enumeration respectively. This indicates that the anaerobic bacteria
analyses for five soil samples after the operation of en- were not the dominant bacteria in contaminated areas due
hanced aerobic bioremediation system. Results show that to the change of oxidation-reduction potential in these
significant amount of total heterotrophs (>105 cells/g soil) areas from anaerobic to aerobic conditions.

Table 4 Concentrations of BTEX and indicating parameters in monitor wells after the operation of enhanced aerobic bioremediation system

Monitor well MW1 MW2 MW3 MW4 MW5

Location High Mid Down Edge BK

Distance from MW1 0 200 300 415 –
Benzene (µg/L) 762 124 5 0.4 BDL
Toluene (µg/L) 731 78 1.3 BDL BDL
Ethylbenzene (µg/L) 458 65 2 0.1 BDL
m+p-Xylene (µg/L) 441 76 2.6 0.1 BDL
o-Xylene (µg/L) 356 71 6.8 0.5 BDL
Total BTEX (µg/L) 2748 414 11.4 1.1 BDL
DO (mg/L) 0.1 1.6 2.0 2.4 2.8
Nitrate (mg/L) 0.16 1.7 2.8 4.1 6.2
Total iron (mg/L) 11.3 6.9 1.2 0.7 0.6
Ferrous iron (mg/L) 10.7 5.6 0.2 0.12 0.1
Sulfate (mg/L) 2 13 10.6 12 15
Sulfide (µg/L) 12 1.8 2.1 2.3 2.6
Carbon dioxide (mg/L) 145 176 86 67 54
Methane (mg/L) 12 6.1 0.08 0.05 0.07
pH 6.6 6.6 6.7 6.7 6.9
Redox potential (mV) –185 45 122 158 196
Ammonia nitrogen (mg/L) 1.4 2.3 1.8 2.4 2.6
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Phosphate (mg/L) 1.1 0.96 1.2 1.3 1.6

Temperature (°C) 24.7 24.2 24.1 24.3 24.2
c.

Methanogen (cells/g) 4.4 × 103 (SB1) 2 (SB2) BDL (SB3) BDL (SB4) BDL (SB5)
Total heterotrophs (cells/g) 4.5 × 105 (SB1) 8.4 × 105 (SB2) 7.1 × 105 (SB3) 4.9 × 104 (SB4) 3.1 × 104 (SB5)
.a

Total anaerobes (cells/g) 3.8 × 104 (SB1) 1.3 × 102 (SB2) 1.6 × 102 (SB3) 1.2 × 102 (SB4) 1.0 × 102 (SB5)
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No. 6 Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation 869

Table 5 Percentage of contaminant removal for each compound between monitor wells after enhanced aerobic bioremediation process

Benzene (%) Toluene (%) Ethylbenzene (%) m+p-Xylene (%) o-Xylene (%) Total BTEX (%)

MW1–MW2 83.7 89.3 85.8 82.8 80 85

MW1–MW3 99.3 99.8 99.6 99.4 98.1 99

Table 6 Calculated first-order natural attenuation rate for each compound between monitor wells after enhanced aerobic bioremediation process

Benzene (day−1 ) Toluene (day−1 ) Ethylbenzene (day−1 ) m+p-Xylene (day−1 ) o-Xylene (day−1 ) Total BTEX (day−1 )

MW1–MW2 0.0101 0.0124 0.0109 0.0098 0.009 0.0105

MW1–MW3 0.0182 0.0229 0.0197 0.0186 0.0161 0.0188

Fig. 6 Variations in total BTEX concentrations in monitor wells located

in cross section line as MW6-MW7-MW2-MW8-MW9, before and after
the operation of the enhanced aerobic bioremediation system .

Fig. 5 Results of microbial enumeration analyses for five soil samples

after the operation of the enhanced aerobic bioremediation system. of the BTEX reduction in those wells, especially at the
sides of the plume. As the plume spread in width due
to dispersion, oxygen in the uncontaminated groundwater
Results also show that the methanogen populations mixed with BTEX at the plume sides, and thus enhanced
detected before and after the operation of enhanced aerobic biodegradation. This caused the semi-circular shapes of
bioremediation was in SB1 were similar. However, a the mass flux results at the cross section (Fig. 6) and the
low methanogen population was observed in SB2 after elongated shape of the plume (Fig. 1).
the operation of enhanced aerobic bioremediation process Because bioremediation rates under aerobic conditions
(Tables 1 and 4). This also reveals that the injection of are generally higher than those under anaerobic conditions,
air affected the redox conditions and caused the decrease air injection into the subsurface would enhance the BTEX
in methanogen in SB2. Field results reveal that the aer- biodegradation rates. Results from the field investiga-
obic biodegradation patterns were the dominant intrinsic tion also reveal that the enhanced aerobic bioremediation
biodegradation processes in mid plume and downgradient process caused significant changes in environmental con-
areas. The occurrence of aerobic biodegradation of BTEX ditions. Table 6 shows the calculated first-order decay
due to the air injection can be confirmed by the increased rate for each compound between monitor wells after
population of total heterotrophs and decreased population the enhanced aerobic bioremediation process. The total
of total anaerobes in sediments SB2 and SB3 (Table 4). BTEX decay rates were 0.0105 day−1 and 0.0188 day−1
Figure 6 presents the variations in total BTEX con- between MW1 to MW2 and MW1 to MW3, respectively.
centrations in monitor wells located in cross section line Results show that toluene was the most quickly degraded
as MW6-MW7-MW2-MW8-MW9 before and after the compound in BTEX (up to 0.0229 day−1 ), followed by
operation of the enhanced aerobic bioremediation system. ethylbenzene (0.0197 day−1 ), m+p-xylene (0.0186 day−1 ),
Results show that significant drops of the total BTEX benzene (0.0182 day−1 ), and o-xylene (0.0161 day−1 ) be-
concentrations were observed along the cross section line tween MW1 to MW3 (Table 6). The observed decay rates
from MW6 to MW9 after the operation of enhanced for BTEX were much higher than the decay rates obtained
aerobic bioremediation system. This also confirms that before the enhanced aerobic bioremediation process (Table
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the injected air caused the enhanced biodegradation of 3). This indicates that the enhanced aerobic bioremediation
BTEX downgradient of the air injection wells. The limited process caused the change of the treatment mechanisms
c.

spreading of the plume was attributed to the natural atten- from anaerobic biodegradation to aerobic biodegradation.
.a

uation, and aerobic biodegradation was the major cause Increased DO in the groundwater activated the aerobic
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870 Ku-Fan Chen et al. Vol. 22

microorganisms and enhanced the BTEX removal rates. MNA or enhanced aerobic bioremediation systems for the
Effects of enhanced aerobic bioremediation on the varia- remediation of BTEX-contaminated site.
tions in indicating parameters and enhancement of aerobic
biodegradation in mid-plume and downgradient areas in- Acknowledgments
clude: (1) the increase in DO, CO2 , redox potential, nitrate,
This study was funded by CPC Corp., Taiwan, China.
and sulfate; (2) the decrease in pH, dissolved ferrous iron,
Additional thanks to Prof. J. K. Liu from “National” Sun
sulfide, and methane; (3) the increased total heterotrophs;
Yat-Sen University, and Prof. S. C. Chen from “National”
and (4) the decreased total anaerobes in studied areas.
Kaohsiung Normal University, Taiwan, China for their
assistance throughout this project. The views or opinions
4 Conclusions expressed in this article are those of the writers and should
not be construed as opinions of the U.S. Environmental
Natural attenuation is an important process for con- Protection Agency.
taminant mass reduction and plume containment. The
investigation results showed that the intrinsic bioremedia-
tion mechanisms were occurring causing BTEX removal References
through mixed mass reduction processes. Evidences for
the BTEX biodegradation include: (1) decreased BTEX Abu G O, 2008. A study of natural attenuation processes involved
concentrations along the transport path; (2) the depletion in a microcosm model of a crude oil-impacted wetland
of dissolved oxygen, nitrate, and sulfate; (3) the production sediment in the Niger Delta. Bioresource Technology, 99:
4761–4767.
of dissolved ferrous iron, sulfide, methane, and CO2 ; (4)
APHA (American Public Health Association), 2001. Standard
deceased pH in the spill source area and increased pH Methods for the Examination of Water and Waste Water
in iron reducing area; and (5) the preferential removal of (21th ed.). APHA-AWWA-WPCF, Washington, DC.
certain BTEX components along the transport path. Atteia O, Guillot C, 2007. Factors controlling BTEX and chlo-
Results also showed that the BTEX plume is not grow- rinated solvents plume length under natural attenuation
ing and has reached a pseudo-steady-state under mixed conditions. Journal of Contaminant Hydrology, 90: 81–104.
anaerobic and aerobic conditions. This suggested that Balcke G U, Paschke H, Vogt C, Schirmer M, 2009. Pulsed gas
natural attenuation can be used as the remedial option injection: A minimum effort approach for enhanced natural
at the petroleum-hydrocarbon spill site to remediate the attenuation of chlorobenzene in contaminated groundwater.
contaminated groundwater. In the second part of this study, Environmental Pollution, 157: 2011–2018.
enhanced aerobic bioremediation process was applied to Brar S K, Verma M, Surampalli R Y, Misra K, Tyagi R D,
Meunier N et al., 2006. Bioremediation of hazardous wastes
enhance the BTEX biodegradation rates in the mid-plume
– A review. Practice Periodical of Hazardous, Toxic, and
area. Field results also revealed that the operation of Radioactive Waste Management, 10: 59–72.
enhanced aerobic bioremediation caused the change of Chen K F, 2005. Evaluation of the biodegradability of MTBE
anaerobic conditions inside the mid-plume area to aero- in groundwater. Ph.D. Thesis. Institute of Environmental
bic conditions. This variation can be confirmed by the Engineering, “National” Sun Yat-Sen University, Taiwan.
following field observations inside the BTEX plume due Chen K F, Kao C M, Chen T Y, Weng C H, Tsai C T, 2006. Intrin-
to the enhanced aerobic bioremediation process: (1) the sic bioremediation of MTBE-contaminated groundwater at
increase in DO, Eh, nitrate, and sulfate, (2) the decrease in a petroleum-hydrocarbon spill site. Environmental Geology,
dissolved ferrous iron, sulfide, and methane, (3) increased 50: 439–445.
total heterotrophs, and (4) decreased total anaerobes. Devlin J F, Katic D, Barker J F, 2004. In situ sequenced bioreme-
Results also showed that the aerobic biodegradation diation of mixed contaminants in groundwater. Journal of
Contaminant Hydrology, 69: 233–261.
was the dominant degradation processes of BTEX after
Fraser M, Barker J F, Butler B, Blaine F, Joseph S, Cooke C,
the operation of enhanced aerobic bioremediation. Field 2008. Natural attenuation of a plume from an emplaced coal
results showed that the percent of total BTEX removal tar creosote source over 14 years. Journal of Contaminant
increased to 99%, and the calculated total BTEX first-order Hydrology, 100: 101–115.
natural attenuation rates increased to 0.0188% per day, Kao C M, Chen S C, Liu J K, Wang Y S, 2001. Application of
after the application of enhanced aerobic bioremediation microbial enumeration technique to evaluate the occurrence
system from the spill location to the 300 m downgradient of natural bioremediation. Water Research, 35: 1951–1960.
line. Field results from the enhanced aerobic bioremedia- Kao C M, Chen Y L, Chen S C, Yeh T Y, Wu W S, 2003.
tion study indicated that enhanced aerobic bioremediation Enhanced PCE dechlorination by biobarrier systems under
could significantly enhance the BTEX decay rate and different redox conditions. Water Research, 37: 4885–4894.
accelerate the BTEX removal efficiency. Results from Kao C M, Huang W Y, Chang L J, Chien H Y, Hou F, 2005.
Application of monitored natural attenuation to remediate
this study indicate that natural attenuation or intrinsic
a petroleum-hydrocarbon spill site. Water Science and
bioremediation is a very promising technology to ef- Technology, 53: 321–328.
fectively manage this petroleum-hydrocarbon spill site,
cn

Lai K C K, Surampalli R Y, Tyagi R D, Lo I M C, Yan S,

and enhanced aerobic bioremediation is also a promising 2007. Performance monitoring of remediation technologies
technology to enhance the BTEX biodegradation in con-
c.

for soil and groundwater contamination: Review. Practice

taminated groundwater. Knowledge and comprehension Periodical of Hazardous, Toxic, and Radioactive Waste
.a

obtained in this study will be helpful in designing a Management, 11: 132–157.

sc
je
 No. 6 Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation 871

Ling M, Rifai H S, 2007. Modeling natural attenuation with in the subsurface. Journal of Contaminant Hydrology, 70:
source control at a chlorinated solvents dry cleaner site. 173–203.
Ground Water Monitoring and Remediation, 27: 108–121. Sutherland J, Adams C, Kekobad J, 2004. Treatment of MTBE
Maier U, Rügner H, Grathwohl P, 2007. Gradients controlling by air stripping, carbon adsorption, and advanced oxidation:
natural attenuation of ammonium. Applied Geochemistry, Technical and economic comparison for five groundwaters.
22: 2606–2617. Water Research, 38: 193–205.
Neuhauser E F, Ripp J A, Azzolina N A, Madsen E L, Mauro US EPA (US Environmental Protection Agency), 2004. How
D M, Taylor T, 2009. Monitored natural attenuation of to Evaluate Alternative Cleanup Technologies for Under-
manufactured gas plant tar mono- and polycyclic aromat- ground Storage Tank Sites: a Guide for Corrective Action
ic hydrocarbons in ground water: A 14-year field study. Plan Reviewers. EPA/510/R-04-002.
Ground Water Monitoring and Remediation, 29: 66–76. Wu Y W, Huang G H, Chakma A, Zeng G M, 2005. Separation of
Schmidt T C, Schirmer M, Weib H, Haderlein S, 2004. Microbial petroleum hydrocarbons from soil and groundwater through
degradation of methyl tert-butyl ether and tert-butyl alcohol enhanced bioremediation. Energy Sources, 27: 221–232.

cn
c.
.a
sc
je

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