Environmental Pollution 119 (2002) 23–31

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Bioremediation of diesel-contaminated soil with composting

Wan Namkoonga,*, Eui-Young Hwangb, Joon-Seok Parka, Jung-Young Choic
a
Department of Environmental Engineering, College of Engineering, Konkuk University, Seoul 143-701, South Korea
b
Institute of Technology, Kyong-Ho Engineering Co. Ltd., Kuri, 471-722, South Korea
c
Department of Environmental Industry, Shinsung College, Dangjin, 343-861, South Korea

Received 10 May 2001; accepted 7 November 2001

‘‘Capsule’’: Compost and sewage sludge were quite useful in remediating diesel-contaminated soil.

Abstract
The major objective of this research was to find the appropriate mix ratio of organic amendments for enhancing diesel oil
degradation during contaminated soil composting. Sewage sludge or compost was added as an amendment for supplementing
organic matter for composting of contaminated soil. The ratios of contaminated soil to organic amendments were 1:0.1, 1:0.3, 1:0.5,
and 1:1 as wet weight basis. Target contaminant of this research was diesel oil, which was spiked at 10,000 mg/kg sample on a dry
weight basis. The degradation of diesel oil was significantly enhanced by the addition of these organic amendments relative to
straight soil. Degradation rates of total petroleum hydrocarbons (TPH) and n-alkanes were the greatest at the ratio of 1:0.5 of
contaminated soil to organic amendments on wet weight basis. Preferential degradation of n-alkanes over TPH was observed
regardless of the kind and the amount of organic amendments. The first order degradation constant of n-alkanes was about twice
TPH degradation constant. Normal alkanes could be divided in two groups (C10–C15 versus C16–C20) based on the first order
kinetic constant. Volatilization loss of TPH was only about 2% of initial TPH. Normal alkanes lost by volatilization were mainly
by the compounds of C10 to C16. High correlations (r=0.80–0.86) were found among TPH degradation rate, amount of CO2
evolved, and dehydrogenase activity. # 2002 Published by Elsevier Science Ltd.
Keywords: Contaminated soil; Composting; Diesel oil; TPH (Total Petroleum Hydrocarbons); Sewage sludge; Compost; Biodegradation

1. Introduction Although composting of yard wastes, municipal was-

tewater sludge, and municipal solid wastes have been
Soil contamination from leaking underground storage performed for decades, composting of soils con-
tanks (LUSTs) and its adverse effects are major prob- taminated with hazardous materials is still an emerging
lems that we are facing today because LUSTs are ubi- ex-situ biological technology. Composting has been
quitously distributed. Stored fuels consist of various demonstrated to be effective in biodegrading explosives
petroleum hydrocarbons having potential toxic effect to and PAHs (polycyclic aromatic hydrocarbons) in soils
human beings (Wang and Bartha, 1994). Bioremedia- during full-scale applications (USEPA, 1996). Com-
tion is emerging as the most cost-effective treatment posting of soils contaminated with petroleum hydro-
method for hydrocarbon-contaminated soil, especially carbons, especially diesel fuel, has been demonstrated
when the contaminants are medium distillate fuel by only a few researchers (Stegmann et al., 1991; Van
(Wang and Bartha, 1994). Of several forms of treatment Den Munckhof and Veul, 1993).
for excavated soils, composting has advantages over In the composting of contaminated soil, organic
other types of technologies. Advantages include rela- amendments including manure, yard wastes, and food-
tively low capital and operating costs, simplicity of processing wastes are often added to supplement the
operation and design, and relatively high treatment effi- amount of nutrients and readily degradable organic
ciency (Freeman and Harris, 1995; USEPA, 1996). matter in soil (USEPA, 1996). The ratio of con-
taminated soil to organic amendments should be deter-
* Corresponding author. Tel.: +82-02-450-3546; fax: +82-02-454-
mined because an inappropriate ratio may retard or
0428. inhibit microbial activity (Thomas et al., 1992). Addi-
E-mail address: [email protected] (W. Namkoong). tion of organic amendments including sewage sludge or
0269-7491/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.
PII: S0269-7491(01)00328-1
24 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31

compost can facilitate degradation of organic con- Table 1

taminants because they play a role in supplementing Characteristics of soil, sewage sludge, and compost used for this
research
nutrients and carbon source in contaminated soil. Sew-
age sludge and compost may contain abundant nitrogen Soil Sewage Compost
and organic matter and thus have a great potential in sludge
bioremediation (Thomas et al., 1992; LaGrega et al., Water content (%) 13.8 66.0 40.5
1994). Also, sewage sludge and compost have high Field capacity (%) 26.1 76.4 68.4
microbial diversity, with total microbial populations Volatile solids (%) 2.6 45.2 43.0
much higher than fertile soils (Bohn, 1996; Thomas et PH 6.3 7.8 8.4
al., 1992). Since microbes are primary agents for the Cation exchange capacity 17.1 34.3 48.5
(meq/100 g dry matter)
degradation of organic contaminants in soil, increasing Heavy metals Pb 112 80 55
microbial density can accelerate degradation of the (mg/kg dry matter) Zn 409 212 181
contaminants (USEPA, 1998). Hwang et al. (2001) Cu 125 371 87
studied recycling of remediated soil as microbial inocula Ni 113 44 14
and organic amendments for effective composting of Cd NDa ND ND
diesel-contaminated soil. However, little research has a
ND, not detected.
been conducted on the effect of organic amendments on
the composting of diesel-contaminated soil. A great
amount of diesel (5.5109 l) was sold during the first field capacity were 76.4 and 68.4%, respectively. The
half of year 2000 in Korea (http://www.kosanet.or.kr, CEC (cation exchange capacity) of soil used for this
National status of Gas Stations in korea, 2001). research was 17.1 meq/100 g dry soil, which was in the
Although information for diesel-contaminated soil is range of natural soils having CEC value of 10–30 meq/
not currently available in Korea, widespread use of die- 100 g. The CEC of sewage sludge and compost were
sel oil may result in numerous occurrences of diesel- 34.3 and 48.5 meq/100 g dry matter, respectively.
contaminated sites.
2.2. Experimental apparatus

2. Materials and methods Experimental apparatus used for this research con-
sisted of a compost reactor, two CO2 removal traps, a
2.1. Materials humidifier, and a trap for collecting CO2 evolved from
biodegradation (Fig. 1). Carbon dioxide was removed
The materials used for this research include diesel oil, from the incoming air so that CO2 in the exiting air was
soil, sewage sludge, and matured compost. The soil was attributed entirely to decomposition. Most of the CO2
collected from the top 15 cm of the soil surface in the in the incoming air was removed by reaction with soda
campus of Konkuk University. The soil was air-dried lime (Ba(OH)2). Any residual CO2 that passed through
and sieved to pass a 2-mm sieve. The texture of the soil the solid-phase soda lime column was efficiently
was classified as a sandy loam (the portions of sand, silt, removed by reacting with 25-ml sodium hydroxide (4N
and clay of soil were 59.5, 23.0, and 17.5%, respec- NaOH) in a secondary CO2 removal trap. A humidifier
tively). Dewatered sewage sludge was obtained from containing distilled water was used to prevent any aspi-
Nanji publicly owned treatment works in Korea. Com- rated alkali solution from entering the compost reactor
post was obtained from a composting facility at Nanji and to raise the water content of the incoming air to
publicly owned treatment works. Compost was pro- nearly 100% relative humidity at room temperature.
duced from the mixture of food waste and wood chips. This process is to prevent the content in the reactor
Produced fresh compost from the facility was cured for from drying. Carbon dioxide-removed and humidified
about 2 months. air was entered into the 3-l-compost reactor (air-tight
Table 1 shows characteristics of soil, sewage sludge, glass vessel) through a perforated stainless steel bottom
and compost used for this research. As shown in plate. This perforated bottom plate was covered with 5-
Table 1, soil contains organic matter of 2.6%. Sewage mm diameter glass beads. Glass beads were used to
sludge and compost contain significantly large amount supply air evenly and efficiently without channeling and
of organic matter (45.2 and 43.0%, respectively) com- to prevent the perforated plate from clogging with fine
pared with the soil. These analyses indicate that organic particles. Volatile compounds from the reactor were
amendments such as sewage sludge and compost can be collected using a 4-mm internal diameter and a 7-cm
added as an organic matter for composting of soil. long glass tube (Cat. No. 226-01, SKC Inc., Valley View
Water content at field capacity of the soil was 26.1% on Road, Pennsylvania) containing 150 mg of charcoal.
weight basis, which was a typical value of sandy loam. Charcoal tube was replaced to determine volatilization
In case of sewage sludge and compost, water contents at rate at each sampling interval. The tube was packed
 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31 25

Fig. 1. Schematic diagram of experimental apparatus used for this research.

with charcoal (coconut activated carbon), having high Table 2

adsorption capacity for volatile organic compounds and Mix ratio of organic amendments
consisted of a front part of 100 mg and a rear part of 50 Amendments Mix ratioa Remarks
mg. The front and back parts were divided by a small
amount of sponge. If the VOC concentration of the rear Contaminated soil: 1:0.1
sewage sludge 1:0.3
part was higher than 25% of the front part, it was 1:0.5
regarded that absorption capacity of the front part of 1:1
charcoal was breakthrough. Gas sampling time was Sludge only 2000 mgHgCI2kg sample
regulated to avoid breakthrough of charcoal. Evolved Biocide (1:0.5)
CO2 was continuously trapped in a solution of 4 N
Contaminated 1:0.1
NaOH. soil:compost 1:0.3
1:0.5
2.3. Experimental conditions 1:1
Compost only 2000 mgHgCI2/kg sample
Target contaminant of this research was diesel oil, Biocide (1:0.5)
Control Soil only
which was spiked at 10,000 mg/kg sample on a dry
basis. Experimental apparatus was placed in an incu- a
Ratio of contaminated soil to organic amendments on a wet
bator in which temperature was maintained at 20  C to weight basis (see Table 1 for water contents).
minimize the effect of exterior temperature variation.
Water content of soil sample in the reactor was con- to discriminate abiotic degradation portion from total
trolled at 70% of sample field capacity before the input degradation portion (Table 2).
of sample in the reactor and additional water control
was not carried out during experimental period. An 2.4. Analysis
aeration rate of 100 ml/min (200 l/min m3 of soil) was
introduced into the reactor. The ratios of contaminated Samples for GC analysis were prepared by 2-h
soil to organic amendments were 1:0.1, 1:0.3, 1:0.5, and extraction at 200 rpm on a shaker. The ratio of sample
1:1 as wet weight basis (Table 2). Also an amendments- to solvent was 1–5. Extraction recovery efficiency of
only experiment without mixing contaminated soil was TPH by this procedure was 98.7% on average (Hwang
carried out to find the degradation rate of diesel oil in et al., 2000). A 1-ml extract was injected into a gas
sludge alone (sludge-only experiment) and compost chromatograph (Hewlett Packard Model 5890 Series II)
alone (compost-only experiment). To investigate the equipped with an integrator (Hewlett Packard Model
degradation rate of diesel oil in soil alone, a soil-only 3395), a flame ionization detector and HP-1 column (25-
experiment (without mixing organic amendments) was m length0.32-mm internal diameter0.52-mm methyl
also carried out as control run. In the case of the 1:0.5 silicone film thickness). The working calibration curve
mix ratio experiment, a biocide control experiment by for the external standard technique was verified each
addition of HgCl2 of 2,000 mg/kg was also carried out working day. A stock standard solution for TPH was
26 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31

prepared using commercial diesel fuel. Stock standard (triphenylformazan). A 20-g portion of sample was
solutions for n-alkanes (Sigma HSL-15, Sigma chemical mixed with 0.2 g CaCO3. Mixed sample was placed in
co., St. Louis, Montana) and branched alkanes 25-ml screw-cap vial. The amount of sample transferred
(Radian, Bellefonte, Pennsylvania) were prepared using in the vial varied from 1 g to 6 g depending on difference
commercially available standard materials. Measured of dehydrogenase activity of sample. One milliliter of
compounds include normal alkanes ranging from 3% TTC solution and 2.5 ml of distilled water were
C10 to C20 and the branched alkanes such as prist- added into the vial and mixed thoroughly. After 24 h of
ane (2,6,10,14-tetramethylpentadecane) and phytane incubation at 37  C, reduced formazan (red color) was
(2,6,10,14-tetramethylhexadecane). The initial tempera- extracted by adding 10 ml methanol and shaking for 1
ture and temperature progress rate were selected based min. Extracted formazan was filtered through cotton in
on the retention time of the spiked compounds. The a funnel by adding methanol. Methanol was added
initial temperature was kept at 50  C for 1 min. Temp- continuously until the red color of cotton would be dis-
erature was increased at 25  C/min to final temperature appeared. Filtrate was diluted to 100-ml by adding
of 300  C, and maintained at that temperature for 1 min methanol. A TPF standard solution was prepared by
in order to ensure that the column was clean. The dissolving triphenyl formazan (Sigma, St. Louis, Mon-
injection port and detector temperatures were 250 and tana) in methanol. The color intensity of filtrate was
300  C, respectively. Hydrogen gas and air flow rates for determined using spectrophotometer (Metertek SP-830,
the flame ionization detector were 33 ml/min and 330 MG Scientific, Inc., Pleasant Prairie, Wisconsin) at
ml/min, respectively. Nitrogen carrier gas was delivered 485 nm with methanol as a blank. Dehydrogenase
at a rate of 28 ml/min. activity was expressed in micrograms of formazan per
Carbon dioxide evolved by biological reaction was gram of sample (mg-TPF/g sample).
collected in 4 N NaOH as proposed by Stotzky (1979).
An excess of barium chloride (3N BaCl2) was added to
precipitate the carbonate as BaCO3. After adding a few 3. Results and discussion
drops of phenolphthalein indicator, the samples were
titrated with 1 N HCl. Carbon dioxide-uncollected The effect of a mix ratio of sewage sludge and com-
NaOH was titrated as blank. post on the degradation of diesel oil is presented in
Dehydrogenase activity was used as a broad-spectrum Fig. 2. The correlation coefficients for the kinetic models
indicator of microbial activity in mixtures of soil and indicated that the commonly used first order model
additives. Dehydrogenase activity was measured spec- describes the degradation of TPH and n-alkanes with
trophotometrically using characteristics of TTC (2,3,5- high correlation coefficients (Table 3). The first order
triphenyltetrazolium chloride) reduction to TPF kinetic model was linearly regressed with relationship
between operational period and natural log value of
TPH concentration. Rapid degradation of TPH was
observed in the early stage (within 15 days) of reaction
in all experiments, but especially in the sewage sludge
amendment experiments. Following the rapid degrada-
tion of TPH within 15 days, residual TPH was degraded
slowly compared with the early stage. Difference in
TPH degradation rate depending on time was due to the
rapid degradation of n-alkanes in TPH at the early
stage, which was evidenced by the first order kinetic
constants (Table 3). Heavier molecular weight com-
pounds are more resistant to degradation resulting in a
decrease in biodegradation rate (van Zyl and Lorenzen,
1999).
The first order degradation rate of n-alkanes was sig-
nificantly greater than TPH regardless of the kind and
the amount of added organic amendments (Table 3),
which indicated that normal alkanes were preferentially
degraded compared with other components in TPH (De
Jonge et al., 1997; Frankenberger, 1992; Thomas et al.,
1992). Fig. 3 shows the relationship of the first order
Fig. 2. Volatilization-corrected TPH degradation depending on the
degradation rate constants the between sum of n-
mix ratio of organic amendments. (a) Amendment=sludge; (b): alkanes and TPH. Linear regression analysis indicated
Amendment=compost. that the degradation rate constants of the sum of
 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31 27

Table 3
Estimation of degradation kinetic parameters based on the first order
kinetic model in sewage sludge and compost addition experiments

Amendments Mix ratioa Materials kb rc Half-life

(day)

Sewage sludge Sludge-only TPH 0.015 0.92 6.6

n-alkanesd 0.183 0.96 3.8
1:0.1 TPH 0.072 0.96 9.6
n-alkanes 0.113 0.67 6.1
1:0.3 TPH 0.120 0.98 5.8
n-alkanes 0.272 0.96 2.6
1:0.5 TPH 0.124 0.98 5.6
n-alkanes 0.252 0.97 2.8
1:1 TPH 0.093 0.99 7.5 Fig. 3. Relationship of the first order degradation rate constants
n-alkanes 0.188 0.87 3.7 between TPH and sum of n-alkanes.

Compost Compost-only TPH 0.105 0.92 6.6

n-alkanes 0.182 0.96 3.8
the mix ratio of 1:0.5 of contaminated soil to compost
1:0.1 TPH 0.036 1.00 19.2 (k=0.113/day, percent degradation=98.4%; Tables 3
n-alkanes 0.068 0.90 10.2 and 4) as a result of ANOVA (P40.05). First order
1:0.3 TPH 0.076 0.96 9.1 degradation rate constant for TPH at 1:0.5 mix ratio
n-alkanes 0.109 0.98 6.4 experiment was about three times greater than that of
1:0.5 TPH 0.113 0.94 6.2
n-alkanes 0.152 0.98 4.6
soil-only experiment. Higher mix ratio did not necessa-
1:1 TPH 0.104 0.97 6.7 rily increase the degradation rate of TPH. Thomas et al.
n-alkanes 0.179 0.98 3.9 (1992) suggested that the addition of organic amend-
ments could increase the degradation rate of target
– Soil-only TPH 0.037 0.97 18.7 contaminants, but might inhibit degradation the rate
n-alkanes 0.052 0.092 13.4
when an excessive amount of organic amendment was
a
The value implies the ratio of contaminated soil to sewage sludge added. These research results also indicate that excessive
or compost. addition of sewage sludge and compost retarded degra-
b
Sum of individual n-alkane ranging from C10 to C20. dation rate of the target contaminants. The TPH
c
k=the first order kinetic constant.
d
r=correlation coefficient.
degradation rate constant at the sludge-only experiment
was the same as that of the compost-only experi-
ment (Table 4). At low mix ratios; however, degradation
n-alkanes were significantly correlated to those of TPH. rate constants of TPH for sewage sludge experiments
Degradation rate of n-alkanes was about two times differed significantly from those for compost amend-
greater than that of TPH (Fig. 3). Quantitative data ment experiments as a result of ANOVA (P40.05). At
about preferential degradation of n-alkanes have not the mix ratio of 1:0.1 and 1:0.3 of contaminated soil to
been presented in other research. sewage sludge, TPH degradation rate constants were
Negligible degradation of TPH occurred in biocide about two times larger than those of experiments with
treatment, which means that most of the degradation compost at the same mix ratio. This result might be
could be attributed to biodegradation. Total volatiliza- caused by the difference in the amount of readily
tion loss in all experiments was in the range of 0.9– degradable organic matter between the two amendment
2.6%, which indicated that volatilization in the removal materials. The amount of readily degradable organic
of diesel oil in contaminated soil was very small com- matter in compost is relatively small, compared with
pared with biodegradation (Table 4). that of sludge, because compost is biologically stable
Of sewage sludge addition experiments, degradation material. At high mix ratios, however, no significant
of TPH within 30 days was the greatest (98.1%) at the difference in degradation rate of TPH was observed
mix ratio of 1:0.3 and 1:0.5 (Table 4) as a result of between the two amendment materials as a result of
analysis of variation (ANOVA; P40.05). Percent ANOVA (P40.05).
degradation of TPH in the soil-only experiment was The carbon source in the amendment materials must
only 64.5%. The first order degradation rate constants not represent a preferential carbon source that preempts
also indicated that the most active degradation of TPH degradation of the target contaminants (LaGrega et al.,
occurred at the mix ratios of 1:0.3 (k=0.120/day) and 1994). In other words, when the added carbon source
1:0.5 (k=0.124/day) of contaminated soil to sewage was preferentially degraded over the target compounds,
sludge (Table 3). microbial activity for degrading the target contaminants
When matured compost was used as amendment, the may be inhibited (Thomas et al., 1992; LaGrega et al.,
most active degradation of TPH was also observed at 1994; Cookson, 1995). In this research, sewage sludge
28 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31

Table 4 amendments (Fig. 4). The first order degradation rates

Percent removal, volatilization, and degradation of TPH during 30 for n-alkanes from C10 to C15 were in the range of
days
0.37/day to 0.54/day, whereas n-alkanes from C16 to
Amendments Mix ratioa Removal Volatilization Degradation C20 showed degradation rates from 0.18/day to 0.24/
day. Mean degradation rates of pristine (2,6,10,14-
Sewage sludge 1:0.1 88.1 2.1 86.0
1:0.3 99.0 0.9 98.1
tetramethylpentadecane) and phytane (2,6,10,14-tetra-
1:0.5 99.5 1.4 98.1 methylhexadecane) were 0.12/day and 0.15/day, respec-
1:1 95.9 1.4 94.6 tively. Results found from this research may be
Sludge-only 98.2 2.4 95.8 explained by the difference of aqueous solubility of
alkanes. According to Gustafson et al. (1996), mean
Compost 1:0.1 69.3 2.2 67.1
1:0.3 95.1 2.0 93.1
solubility of n-alkanes of C10 to C15 is in the range of
1:0.5 99.6 1.2 98.4 0.052 mg/l to 0.007 mg/l, and C16 to C20 ranged from
1:1 99.1 2.0 97.1 510 5 mg/l to 310 7 mg/l. The difference of aqueous
Compost-only 97.2 2.6 94.6 solubility may result in different degradation rate
because non-aqueous-phase liquid (NAPL) such as die-
– Soil-only 66.6 2.1 64.5
sel oil is mainly presented as a film layer on soil particles
a
The value implies the ratio of contaminated soil to sewage sludge or as dispersed droplets (De Jonge et al., 1997). The
or compost. microorganisms are present near the NAPL-water
interfaces, and the degradation rate of NAPL is con-
and compost added as a carbon source did not act as trolled by aqueous solubility. According to Lee et al.
competing energy sources, but caused an increase of (1997), n-alkanes from C12 to C15 in mineral fine
degradation rate of the diesel oil. This fact was deduced amended seawater were not detected after 56 days, while
indirectly from high degradation rates of TPH from the n-alkanes over C16 remained in the sample. De Jonge et
organic amendment addition experiments compared al. (1997) reported that the residual concentrations of n-
with the soil-only experiment. alkanes decreased with increasing carbon number,
Stegmann et al. (1991) evaluated the effect of compost reflecting that the carbon number of the n-alkanes
addition on the composting of diesel-contaminated soil. influenced the biodegradation rate.
They reported that the maximal oxygen consumption Volatilization of individual n-alkanes decreased as the
rate and the lowest final TPH concentration were mix ratio of contaminated soil to sewage sludge
observed at the mix ratio of 1:0.5 (contaminated soil to increased. The sum of volatilization of n-alkanes in case
compost) on a dry weight basis. In this research, the mix of the soil-only experiment and 1:0.1 mix ratio experi-
ratio of 1:0.5 on a wet weight basis showed the highest ment was higher than those of other experiments
percent degradation of TPH. This ratio corresponded to (Fig. 5). Normal alkanes were volatilized continuously
the ratio of 1:0.3 on a dry weight basis, which is smaller during 30 days at the soil-only experiment and 1:0.1 mix
than that of Stegmann et al. (1991). The reasons for this ratio experiment. For other mix ratio experiments
difference in mix ratio may include the kinds of compost and sludge-only experiment, n-alkanes were lost by
and compost maturity. Therefore, a feasibility study volatilization mainly during the first 4 days. At compost
should be carried out to find optimum mix ratio of addition experiments, similar results were observed
compost to contaminated soil. Result from this research (data were not presented); the reasons for a different
present important engineering points because the
amount of compost added is relatively small and
thereby volume of contaminated soil to be treated at the
same area can be increased. Sludge and compost offer
good nutrient sources for microorganisms (Minna
Laine and Jørgensen, 1996). The bulky structures of
the organic material in compost open and stabilize the
structure of contaminated soils in most cases (Minna
Laine and Jørgensen, 1997).
It is commonly expected that degradation rate of
individual n-alkane would decrease with the increase
of its molecular weight or number of carbons. But, an
obvious difference of degradation rates depending on
the molecular weight was not observed in this research.
Fig. 4. Comparison of the first order degradation rate constant for
Rather, degradation rate of individual n-alkanes could individual hydrocarbons [circles mean average value, bars imply stand-
be divided in the two groups (C10–C15 versus C16– ard errors, Pr : Pristane(2,6,10,14-tetramethylpentadecane), Ph:Phy-
C20) regardless of the kind and the amount of organic tane(2,6,10,14-tetramethylhexadecane)].
 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31 29

Fig. 6. Variation of cumulative CO2 in off-gas and dehydrogenase

activity depending on the mix ratios of sewage sludge and compost.

Table 5
Matrix of correlation coefficients for the parameters used in this
research

TPH Cumulative Dehydrogenase

degraded CO2 activity

TPH degraded 1 0.86 0.82*

Fig. 5. Variation of cumulative n-alkanes in off-gas depending on the CO2 1 0.80*
mix ratio of sewage sludge. Dehydrogenase activity 1
*
Significant at 0.01 probability level (P=0.01).

volatilization pattern depending on mix ratio include

adsorption capacity of organic amendments and degra-
dation rate of individual n-alkanes. As sewage sludge evolution at early stage was due to the rapid degrada-
and compost has relatively high adsorption capacity tion of TPH at the same period (Fig. 2). The cumulative
compared with soil, these may prevent low molecular amount of CO2 evolved shows more distinctly the effect
weight n-alkanes from volatilization at high mix ratio of organic amendments on TPH degradation (Fig. 6).
experiments. Also, rapid degradation of n-alkanes at Excess addition of sewage sludge and compost did not
high mix ratio experiments influenced volatilization loss necessarily enhanced CO2 evolution rate. Although
indirectly. Normal alkanes in volatilized TPH were total amount of CO2 evolved at the 1:0.1 mix ratio
mainly consisted of components in the range of C10 experiments was the lowest among organic amendments
(normal decane) to C16 (normal hexadecane). Volatili- addition experiments, it was about two times greater
zation loss of n-alkenes, ranging from C10 to C14, was than that of soil-only experiment.
significantly larger than that of C15 and C16. This phe- Dehydrogenase activity matched fairly well with the
nomenon may be caused by the difference in vapor amount of cumulative CO2 in off-gas (Fig. 6). Dynamic
pressure of n-alkanes. De Jonge et al. (1997) reported increases of dehydrogenase activity were monitored for
that n-alkanes ranging from C16 to C20 were not lost the first 15 days at the mix ratios of 1:0.3, 1:0.5, and 1:1
by volatilization. Bengtsson et al. (1998) reported that for sludge amendments experiments. Therefore, dehy-
hydrocarbons corresponding up to C13–C14 originating drogenase activity may be used as a parameter repre-
from light fuels were found in the off-gas during the senting microbial activity. Martens et al. (1992)
composting of oily sludge. reported that the activity of soil enzymes may be inhib-
In general, CO2 evolution rate has been used as an ited by addition of certain organic amendments such as
index representing microbial activity, because CO2 is a sewage sludge and compost since they contain a sig-
by-product from organic compound degradation. At nificant amount of metals. Increase in microbial activity
sewage sludge addition experiments except 1:0.1 mix in this research, as measured by dehydrogenase activity,
ratio experiment, CO2 evolution increased dramatically indicates that the organisms in sewage sludge and com-
for the first 4 days (Fig. 6). Dramatic increase of CO2 post are metabolically active and may contribute to the
30 W. Namkoong et al. / Environmental Pollution 119 (2002) 23–31

biodegradation process of TPH (Cole et al., 1995). Lar- Acknowledgements

ger activity observed in sludge and compost amended
soils suggests that these materials can be an effective This work was supported by GRANT No. 971-
and inexpensive microbial inoculant as well as a nitro- 1202-008-1 from the Korea Science and Engineering
gen-organic matter source. Foundation. Authors acknowledge Korea Science and
Table 5 shows the correlation coefficients among TPH Engineering Foundation for providing an opportunity
degraded, the cumulative amount of CO2 evolved and to conduct this research.
the dehydrogenase activity. Degradation of TPH was
significantly related to microbial respiration as meas-
ured by CO2 evolution (r=0.86, P40.01). High positive References
correlation was also found between TPH degraded and
the dehydrogenase activity (r=0.82, P40.01). Sig- Bengtsson, Å, Quednau, M., Haskå, G., Nilzén, P., Persson, A.,
nificant positive correlation between the amount of CO2 1998. Composting of oily sludges—degradation, stabilized residues,
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