Journal of Chromatography A, 1122 (2006) 222229

Chemical characterization of odorous gases at a landfill site

by gas chromatographymass spectrometry
Faruk Dincer , Mustafa Odabasi, Aysen Muezzinoglu
Department of Environmental Engineering, Dokuz Eylul University, Kaynaklar Campus, 35160 Buca-Izmir, Turkey
Received 17 January 2006; received in revised form 12 April 2006; accepted 18 April 2006
Available online 12 May 2006

Abstract
The composition of odorous gases emitted from a municipal landfill in the city of Izmir, Turkey was investigated using gas chromatographymass
spectrometry, and these data were examined in relation with the odor concentrations. Several volatile organic compounds (VOCs) were identified and
quantified at five sampling sites in May and September 2005. Detected VOCs were monoaromatics (0.0947.42 g m3 ), halogenated compounds
(0.00162.91 g m3 ), aldehydes (0.0138.55 g m3 ), esters (0.017.54 g m3 ), ketones (0.0367.60 g m3 ), sulfur/nitrogen containing compounds (0.035.05 g m3 ), and volatile fatty acids (VFAs) (0.0543.71 g m3 ). High levels of aldehydes (propanal up to 38.55 g m3 ) and
VFAs (formic acid up to 43.71 g m3 ) were measured in May. However, VOC concentrations were relatively low in September. The monoaromatics and halogenated compounds were the abundant VOCs in landfill air for the both sampling periods. The benzene-to-toluene (B:T) ratio at the
landfill site was significantly lower than urban areas indicating the presence of higher amounts of toluene in landfills compared to traffic exhaust
rich urban areas. A statistically significant linear relationship was found between odor concentrations determined by olfactometry and total VOC
concentrations. The relationships of odor concentrations with the different groups of chemicals were also examined using a step-wise multiple
regression analysis. It was found that the concentrations of aldehydes, ketones, and esters are the best estimators, explaining 96% of the variability
in odor concentrations (r2 = 0.96, n = 10, P < 0.01).
2006 Elsevier B.V. All rights reserved.
Keywords: Odor concentration; Olfactometry; Volatile organic compounds; Landfill odors; GCMS; Benzene-to-toluene ratio

1. Introduction
Municipal solid waste (MSW) landfills are potential sources
of offensive odors creating annoyance in urban areas [1]. Odor
pollution has become a growing concern during the last decades
for urban communities located near or downwind of MSW
landfills. The annoying odors released to the atmosphere from
landfills may cause decreased quality of life and possibly more
negative consequences on human health and welfare [2].
Landfill gases are generated naturally by anaerobic decomposition of wastes. Summer is the critical season for such processes
as the higher temperatures and richer organic matter in the waste
composition favor anaerobic processes leading to waste decomposition. Landfill gases are mainly composed of methane and
carbon dioxide. They also include some non-methane volatile

Corresponding author. Tel.: +90 232 453 0922; fax: +90 232 453 0922.
E-mail address: fdincer@deu.edu.tr (F. Dincer).

0021-9673/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2006.04.075

organic compounds (VOCs) [3]. Although the amounts of VOCs

are usually below 1% (by volume) of the total emissions, their
adverse effects on the environment are not negligible. For example, a range of chlorofluorocarbon compounds contribute to
both stratospheric ozone depletion and greenhouse effect [4].
Prolonged exposure to the landfill gases containing benzene,
toluene, and xylenes (BTX) and chlorinated hydrocarbons can
cause severe health problems especially on landfill operators
[5]. Alkylbenzenes, limonene, certain esters, and organosulfur
compounds are mainly responsible for odor nuisance [6].
Odor measurement techniques have been based on sensory
analysis using human nose as a detector. Compared to the human
nose, many of the chemical detectors are not as sensitive for the
odor active compounds [7]. Olfactometry based on the human
perception capacity is the most common method for measuring odor concentrations. In this method, odor measurement is
carried out by presenting a sample of odorous air in a range of
dilutions using neutral air to an independent panel of selected
and trained persons, and statistically treating the responses from

F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

the panelists for odor detection. Dilutions are prepared using

an olfactometer, and results are evaluated according to certain
protocols such as the CEN methodology [8]. Gas chromatography (GC) in connection with various detectors, especially
mass spectrometry (MS) has been applied for the characterization of the chemical composition of odorous gas samples
[9].
Davoli et al. [10] reported an analytical approach for characterization of odorous VOCs by solid phase microextraction
(SPME) followed by GCMS in landfills for a wide range
of compounds (i.e., from highly polar volatile fatty acids to
non-polar hydrocarbons). Zou et al. [5] conducted a study to
characterize the ambient VOC levels in different seasons in a
landfill in South China. They reported high levels of benzene,
toluene, and chlorinated VOCs. However, their study did not
cover odor concentrations. The relationship between odor and
chemical concentrations was investigated by Defoer et al. [11]
for vegetable, fruit, and garden composting plants and for the
emissions of an animal rendering plant treated by bio-filtration.
These studies compared the profiles of odor concentrations and
chemical concentrations of compounds in different chemical
classes.
The characterization of VOCs [10] and odor assessment
based on the dispersion of odors [1] at landfills were previously
reported. However, there are no studies in the literature investigating the relationship between landfill odor and VOC concentrations. The objective of the present work was to investigate the
relationship between landfill odor and VOC concentrations at
the landfill site of Izmir, Turkey. Samples were collected at five
sampling points in May and September 2005. Odor levels were
measured by olfactometry and the chemical concentrations were
determined by GCMS following thermal desorption. Measured
odor and VOC concentrations were analyzed statistically and
discussed.
2. Materials and methods
2.1. Site description
Harmandal MSW site is the main landfill in Izmir. It has
been in operation since 1990 and receives commercial, industrial, and municipal wastes. The capacity of the landfill is
3000 t day1 of domestic, medical, and industrial wastes and
wastewater treatment sludge. The site does not accept hazardous
wastes.
The field sampling was conducted on May 6 and September
1, 2005 to represent the beginning and end of the hot and dry
summer season in the area having a typical Mediterranean climate. The average temperatures were 19 C in May and 25 C
in September and the relative humidity was 55% in both May
and September sampling days. Same five sampling points were
visited at active burial areas in May and September sampling
periods. Sites 1 and 2 were selected to represent the areas where
thickened sludge from the Izmir municipal wastewater treatment
plant and the medical wastes were disposed, respectively. The
other three sites were at the domestic solid waste disposal area.
Site 3 was the raw waste collection and classification area of

223

the municipal wastes. At the waste classification site there was

heavy truck traffic and machinery operations were active. All
three of the municipal waste burial areas were selected to represent different stages and ages of solid waste management.
2.2. Sampling and analysis
Olfactometry and thermal desorption followed by GCMS
were used to determine the odor and volatile organic compound
concentrations of the collected samples.
2.2.1. Sampling method
Three samples were collected from underneath a specially
designed hood at each sampling point from the air adjacent to the
surface of the landfill covers. Sampling was carried out following
recommendations described in the European Standard EN 13725
[8]. Air samples were drawn into 5 l Nalophan bags using a
special sampler working with the lung principle. The sampler
draws the air directly into the bag by evacuating the tightly closed
atmospheric pressure vessel in which it was placed. Odor and
taste free bags that are impermeable to water and organics were
used in sampling only for once. Polytetrafluoroethylene (PTFE)
sampling tubes were used as input and connection lines. Samples
were transported to the olfactometry laboratory and analyzed
within 24 h.
2.2.2. Olfactometric analysis
The odor concentrations of the samples were measured by
dynamic olfactometry. The tests were carried out inside an odorfree, clean laboratory with selected and trained panelists. Each
sample was diluted in the olfactometer (model TO7, ECOMA,
Honigsee, Germany) several times differing from each other
by a factor of two and presented to the panelists three times.
Dilutions were made using odor-free air supplied by a compressor fitted with carbon filters and an air dryer. The olfactometer
is a computer controlled semi-automatic instrument with four
panel member places and computes the odor concentration by
means of a special computer program based on the perception
response data of panelists. This method employs a yes/no technique and determines how many times a sample must be diluted
with odor-free air to be at the threshold of detection by 50%
of the panel. At this instance the number of required dilution
defines the odor concentration in odor units per cubic meter
(OU m3 ).
2.2.3. Chemical analysis
Grab sampling by Nalophan bags has been commonly used
to collect gas samples. Samples collected in bags are either
directly introduced to the analytical systems or concentrated
using techniques like solid phase micro extraction (SPME) and
adsorbent tubes-thermal desorption (TD). Some recent applications using grab sampling with Nalophan bags include the
analysis of odorous gas emissions from composting plants (gas
sample-proton transfer reaction-mass spectrometry) [12], waste
gases and landfill gases (SPME-GCMS) [10,13,14], VOC
emissions from apple tree (TD-GCMS) [15], VOCs emissions
from moss roses (solidliquid extraction-GCMS) [16], fig tree

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F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

emissions (solidliquid extraction-GCMS) [17], volatiles from

maize (solidliquid extraction-GC-FID) [18], mushroom composting emissions (TD-GCMS) [19]. The use of Nalophan
bags for odor sampling is recommended by the European Standard EN 13725 [8] due to their inertness. A recent study indicated
that gas mixtures containing ppbv concentrations of several chlorinated and aromatic hydrocarbons could be safely stored for
several days in Nalophan bags without any significant loss [20].
In the present study, gas samples were collected into Nalophan
bags and were transported to the laboratory. Then, gases were
passed through the adsorbent tubes via silicone tubing connected to a vacuum pump (Rena 301, Rena OEM, France).
Sampling flow rate and sample volume were 100 ml min1 and
23 l, respectively. The flow rate was measured using a rotameter (Gilmont, Barnant Inc., USA). The rotameter calibration was
checked occasionally (at three flow rates in duplicate, n = 6)
using a primary standard (soap-bubble meter). The average percent difference between two flow meters was <2.5%. Duplicate
tubes obtained from each sampling bag were separately analyzed
to determine the concentrations of volatile fatty acids (VFAs)
and volatile organic compounds, respectively. The sample tubes
were refrigerated and analyzed within 13 days as recommended
[21].
Glass adsorbent tubes (6 mm O.D., 17.8 mm length) were
prepared in the laboratory according to the ambient air sampling methods recommended by USEPA [22]. Each tube was
packed at the upstream (sampling) end with 3 mm silanized
glass wool followed by a series of sections of 150 mg Tenax TA
(60/80 mesh) (Supelco, Bellefonte, PA, USA), 3 mm silanized
glass wool, 100 mg Carboxen 1000 (Supelco, Bellefonte, PA,
USA) and finally 3 mm silanized glass wool at the downstream
end. Filled tubes were conditioned at 260 C for 1 h with a
50 ml min1 reverse flow (opposite to the sampling direction) of
high purity nitrogen prior to use. Ends of the conditioned tubes
were first closed with PTFE caps and each tube was placed into
tightly capped special tube containers prior to use and after sampling. Silica gel and activated charcoal were placed to the bottom
section of the tube containers for humidity and contamination
control, respectively.
Samples were analyzed with a gas chromatograph (GC) (Agilent 6890N, Agilent, Wilmington, DE, USA) equipped with
a mass selective detector (Agilent 5973 inert MSD, Agilent,
Wilmington, DE, USA) and a thermal desorber (Tekmar, Aerotrap 6000, USA). The thermal desorber was modified by replacing the original fused silica transfer line (0.32 mm I.D.) causing
flow restriction through the GC inlet with a glass-lined inert
steel tubing (0.7 mm I.D., Alltech). The cryogenic internal trap
operating with liquid nitrogen was replaced with an adsorbent
(100 mg Tenax, Supelco, Bellefonte, PA, USA) filled ambient
trap. The cooling for the internal trap was provided by a vacuum
pump drawing air at room temperature through the liquid nitrogen line at a rate of 15 l min1 . VOC samples were desorbed for
5 min at 225 C using helium flow at the rate of 40 ml min1 .
Internal trap temperature during sample desorption was 35 C.
The trap was desorbed for 1 min at 240 C. Then, it was baked
for 10 min at 250 C. Valve oven and transfer line temperature
of the thermal desorber was 200 C.

The chromatographic column was HP5-MS (30 m, 0.25 mm,

0.25 m) and the carrier gas was helium at 1 ml min1 flowrate
and 36 cm s1 linear velocity. The split ratio was 1:40. The
inlet temperature was 240 C. Temperature program for VOCs
was: initial oven temperature 40 C, hold 3 min, 40120 C
at 5 C min1 , hold 1 min. Temperature program for VFAs
was: initial oven temperature 50 C, hold 1 min, 50225 C at
35 C min1 , hold 2.5 min. Ionization mode of the MS was electron impact (EI). Ion source, quadrupole, and GC/MSD interface
temperatures were 230, 150, and 280 C, respectively. The MSD
was run in selected ion monitoring mode. Compounds were identified on the basis of their retention times (within 0.05 min of
the retention time of calibration standard), target, and qualifier
ions. Identified compounds were quantified using the external
standard calibration procedure.
Five levels (0.4, 2, 5, 10 and 20 g ml1 ) of VOC solutions
were prepared in methanol as the calibration standards. Five
levels of standard solutions with varying VFAs (i.e., 12, 30, 60,
180, and 300 g ml1 for acetic acid) were prepared in deionized (DI) water. Thermal desorption tubes used for calibration
(150 mg Tenax TA + 100 mg Carboxen 1000) were loaded by
spiking with 1 l of the calibration standards. Then, the standard loaded tubes were run at specified conditions to calibrate
the analytical system (Thermal desorber-GCMS) [22]. In all
cases linear fit was good with r2 > 0.99.
2.3. Quality control and quality assurance
Instrumental detection limits for VOCs (5 pg for a split ratio
of 1:40) were determined by linear extrapolation from the lowest
standard in the calibration curve using the area of a peak having a
signal/noise ratio of 3. Six blank thermal desorption tubes (three
for VFAs and three for VOCs) for each sampling period were
analyzed as process blanks in order to determine the level of contamination during sample handling and preparation. The limit of
detection (LOD, pg) of the method was defined as the mean blank
mass plus three standard deviations (LOD = mean blank + 3SD)
[2327]. LOD values ranged between 5-15230 pg and 5-3843 pg
for May and September sampling periods, respectively. Instrumental detection limits were used for the compounds that were
not detected in blanks. In general, VOCs in the samples were
substantially higher than the blanks. Sample quantities exceeding the LODs were quantified and corrected by subtracting the
mean blank amount from the sample amount. For VFA analyses,
no blanks were detected and therefore blank correction was not
necessary.
For three samples a back-up tube was connected in series
with the sample tube during sampling from the Nalophan bags
to check if there was breakthrough. Back-up tubes were found
to contain similar quantities of the compounds as the blanks
indicating that the breakthrough from the sample tubes was not
a problem during sampling.
The system performance was confirmed daily by analyzing
a midrange calibration standard. The relative standard deviation from the initial calibration was <10%. Analytical precision determined from three pairs of duplicate samples ranged
between 2 and 5%.

F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

3. Results and discussion

Table 1
VOC concentrations (ranges (g m3 ) and mean values) at Izmir landfill

3.1. VOC composition and concentrations

In both sampling periods the odorous emissions from the
landfill have contained several compounds. A total of 53 VOCs
were found in May while 48 VOCs in September sampling
periods (Table 1). The measured VOCs were classified as
monoaromatics (e.g. benzene, toluene), halogenated compounds
(e.g. chlorobenzene, trichloroethene), aldehydes (e.g. hexanal,
propanal), ketones (e.g. acetone), VFAs (e.g. acetic acid, formic
acid), esters (e.g. butyl acetate, butyl formate), and S and N compounds (carbon disulfide and acrylonitrile). In May, the most
abundant group was ketones (25% of total VOC concentrations)
followed by monoaromatics (21%), aldehydes (20%), volatile
fatty acids (17%), halogenated compounds (14%), esters (2%),
and S and N compounds (1%). In September, aldehydes had the
highest concentration (37% of total VOC concentrations) and
they were followed by ketones (36%), monoaromatics (13%),
halogenated compounds (6%), VFAs (5%), S and N compounds
(2%), and esters (1%).
Monoaromatics had significant concentrations in both May
and September samples (Fig. 1). Toluene had the highest average
concentration in this group and was exceeded only by formic
acid and propanal in both sampling campaigns.
Benzene-to-toluene (B:T) ratio has been commonly used as
an indicator of traffic emissions. A B:T ratio of 0.5 was reported
from studies on vehicle exhaust [28]. Recent urban air measurements have also showed B:T ratios ranging between 0.27 and 0.5
[2931] (Table 2). Therefore, B:T ratios around 0.5 may indicate that the ambient VOC concentrations are mainly affected
by traffic emissions. However, landfills have significantly lower
B:T ratios (i.e., 0.1 in USA) [32]. Benzene-to-toluene ratios measured in this study were 0.015 and 0.11 in May and September,
respectively indicating the presence of higher amounts of toluene
than benzene in landfills compared to traffic exhaust rich urban
areas (Table 2).
Chlorinated organics in the landfill might be related to the
solvents that are widely used as cleaners and disinfectants in
urban and industrial sources. Sixteen chlorinated compounds
were detected in May and September samples. The average
concentrations of some chlorinated species such as chloroform,
carbon tetrachloride, chlorobenzene, trichloroethene, and tetrachloroethene were 0.08, 0.17, 0.04, 13.06, and 2.37 g m3 ,
respectively (Fig. 1). Tetrachloroethylene is present in the
textiles, dry cleaning workplaces, and chemical manufacturing units. Trichloroethene is used as a degreaser, extraction,
and cleaning solvent for household, commercial, and industrial uses. Thus, their residuals might have reached the landfill
along with the domestic, commercial, and industrial wastes.
Compared to monoaromatic compounds, the concentrations of
chlorinated species were relatively low in May and September
samples.
In May, all VFAs were detected only at the medical waste
burial point of the landfill. Formic and isobutyric acids were the
most abundant volatile fatty acids in the landfill burial points
with the concentrations of 24.22 and 3.56 g m3 , respectively.

225

Formic acid
Acetic acid
Propionic acid
Isobutyric acid
Butyric acid
Isovaleric acid
Valeric acid
Isocaproic acid
Caproic acid
Heptanoic acid
Acrolein
Butanal
Crotonaldehyde
Decanal
Heptanal
Hexanal
Nonanal
Octanal
Pentanal
Propanal
Butyl acetate
Butyl formate
Butyl propionate
Methyl propionate
Vinyl acetate
Benzene
Ethylbenzene
o,m-Xylene
p-Xylene
Styrene
Toluene
1,1,1-Trichloroethane
1,1,2,2-Tetrachloroethane
1,1,2-Trichloroethane
1,1-Dichloroethane
1,1-Dichloroethene
1,2-Dichlorobenzene
1,2-Dichloroethane
1,2-Dichloropropane
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Bromodichloromethane
Bromoform
Carbon tetrachloride
Chlorobenzene
Chloroform
cis-1,3-Dichloropropene
cis-1,4-Dichloro-2-butene
Dibromochloromethane
Iodomethane
Methylene chloride
Tetrachloroethene
trans-1,2-Dichloroethene
trans-1,3-Dichloropropene
trans-1,4-Dichloro-2-butene
Trichloroethene
2-Butanone
2-Hexanone
4-Methyl-2-pentanone (MIBK)
Acetone
Cyclohexanone
Carbon disulfide
Acrylonitrile
Pyridine

May

September

3.4443.71 (24.22)
0.175.34 (1.92)
0.193.52 (1.86)
0.506.61 (3.56)
0.064.39 (2.22)
0.056.05 (2.34)
0.074.99 (1.86)
2.84a
1.372.91 (2.14)
0.258.85 (3.39)
0.482.02 (1.04)
0.431.70 (1.01)
0.050.38 (0.14
0.661.49 (0.97)
0.161.51 (0.73)
0.475.94 (2.59)
0.642.16 (1.57)
0.272.28 (1.54)
0.151.92 (0.75)
4.1638.55 (21.13)
0.127.54 (2.70)
0.030.10 (0.06)
0.11a
N.D.
0.012.29 (0.51)
0.090.59 (0.29)
0.214.94 (2.03)
0.3510.16 (4.33)
0.349.55 (3.59)
0.6714.44 (3.88)
1.5647.42 (18.97)
0.020.05 (0.04)
N.D.
0.050.08 (0.06)
0.00140.01 (0.006)
0.120.37 (0.27)
0.030.08 (0.05)
0.011.22 (0.30)
N.D.
0.0020.01 (0.005)
0.080.40 (0.25)
N.D.
N.D.
0.120.23 (0.17)
0.010.12 (0.04)
0.030.16 (0.08)
0.030.07 (0.05)
N.D.
N.D.
0.0010.02 (0.02)
1.627.95 (4.42)
0.059.16 (2.37)
N.D.
0.0850.09 (0.09)
N.D.
0.1862.91 (13.06)
N.D.
0.040.80 (0.27)
0.030.42 (0.21)
7.9567.60 (37.17)
0.089.13 (3.15)
0.415.05 (1.51)
0.090.20 (0.14)
N.D.

11.10a
N.D.
N.D.
N.D.
N.D.
0.20a
0.37a
N.D.
0.140.34 (0.22)
0.301.30 (0.73)
1.252.66 (1.83)
0.341.33 (0.59)
0.010.15 (0.09)
1.259.42 (3.95)
0.180.64 (0.32)
0.453.55 (1.32)
1.285.01 (2.64)
0.531.42 (0.82)
0.260.87 (0.44)
5.1513.45 (8.49)
0.090.42 (0.21)
0.030.12 (0.05)
0.10a
0.18a
0.081.79 (0.65)
0.341.06 (0.53)
0.150.76 (0.45)
0.221.11 (0.73)
0.151.01 (0.62)
0.130.40 (0.24)
1.5111.18 (4.76)
0.020.10 (0.04)
N.D.
N.D.
0.02a
0.040.70 (0.22)
0.020.09 (0.04)
0.01a
N.D.
0.02a
0.070.21 (0.14)
N.D.
N.D.
0.100.15 (0.13)
0.0090.014 (0.01)
0.030.13 (0.06)
N.D.
N.D.
N.D.
0.020.03 (0.02)
0.682.58 (1.43)
0.021.02 (0.50)
0.11a
N.D.
0.004a
0.111.95 (0.81)
N.D.
0.060.22 (0.10)
0.050.18 (0.08)
11.2028.57 (19.94)
0.004a
0.242.36 (1.15)
0.030.04 (0.034)
N.D.

Data in parenthesis represent the average concentrations; N.D.: not detected.

a Identified only in one sampling site.

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F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

Fig. 1. Seasonal variations of concentrations of monoaromatics, halogenated compounds, aldehydes and ketones, and VFAs.

In September, the concentration of formic acid was relatively

lower and it could be detected at one site only.
High levels of aldehydes and ketones were observed at each
sampling location in May and September with the maximum levels at sampling sites 3 and 4. Propanal has a pungent, suffocating
and unpleasant odor characterizing the landfill gas emissions.
Propanal was found above the odor threshold of 3.6 g m3
[33] at all sampling points.
Some esters and organic S and N compounds were also identified and quantified in this study but the concentrations of these
compounds were relatively low compared to other VOC groups.
For example, concentrations of butyl acetate were 2.70 and
0.21 g m3 in May and September, respectively. Carbon disulfide that has a characteristic odor (vegetable sulfide/medicinal)
had relatively low average concentrations (1.51 g m3 in May

Table 2
Comparison of average benzene and toluene levels (g m3 ) and B:T ratios in
ambient air at selected locations
Benzene

Toluene

B:T

Site

Reference

0.23
0.53

18.97
4.76

0.015
0.11

Izmir (landfill)
Izmir (landfill)

3.31
37.6
52.8
33.8

15.39
102
528
62

0.27
0.37
0.1
0.5

Izmir (urban)
Izmir (urban)
USA (landfill)
Guangzhou (urban)

This study (May)

This study
(September)
[29]
[31]
[32]
[30]

and 1.15 g m3 in September). Acrylonitrile concentrations

were even lower (0.0340.14 g m3 ). Recent studies have
shown that reduced sulfur compounds are important trace components of landfill gases [3436]. Thus, sulfur and nitrogen
containing organic compounds that are not measured in this
study may also be significant in odor characterization.
3.2. Odor and total VOC concentrations
The results of olfactometric and chemical analysis for the
two sampling periods are given in Table 3. The total VOC concentrations presented in Table 3 are the sum of concentrations
of detected compounds. For May samples, olfactometric concentrations varied between 1416 and 116,027 OU m3 with a
mean value of 47,886 OU m3 and the total VOC concentrations
varied between 69 and 258 g m3 (average, 156 g m3 ). For
September samples the olfactometric and total VOC concentrations ranged between 1070 and 111,980 OU m3 (average,
29,684 OU m3 ) and 43101 g m3 (average, 56 g m3 ),
respectively.
Total VOC concentrations in May and September have shown
similar patterns. In September total VOC concentrations were
relatively lower at all sampling locations with slightly decreasing
odor concentrations (Fig. 2, Table 3). A significant decrease in
odor concentration was observed only at Site 5. This decrease
was probably due to the fact that during the May sampling there
was an ongoing waste burial while the site was covered with soil
during the September sampling.

F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

227

Table 3
Concurrent data sets of the olfactometric odor concentrations (OU m3 ) and chemical concentrations (g m3 ) for May and September samples
Sampling point

Odor concentration

Total VOC
concentration

May
1
2
3
4
5

3765
1416
116027
35928
82292

153
219
21939
2050
3215

118
69
258
207
127

September
1
2
3
4
5

3380
1070
111980
29270
2720

400
425
20817
2309
800

56
36
101
43
44

Acids

Aldehydes

Esters

Halogenated
compounds

Monoaromatics

Ketones

S and N
compounds

10
2
13
11
9

0.11
45
38
45
1

18
9
48
34
48

1
0.17
10
5
0.42

74
2
17
5
7

6
4
76
67
13

19
8
68
50
52

1.2
0.6
0.6
0.6
5.2

5
2
6
2
4

N.D.
1
12
2
0.30

19
14
37
18
14

0.26
0.19
1
1
2

5
1
6
3
2

6
5
15
8
3

25
12
29
11
23

1.0
1.9
2.4
0.27
0.29

Fig. 2. Variations of odor and total VOC concentrations in May and September
samples.

An odor control chemical (consisted of nearly 20% calcium

hydroxide) applied onto the landfill sites (Izmir Metropolitan Municipal Waste Management Authority, 2005) during the
period starting with mid-April and ending in September 2005.
This application has focused mainly on sludge and medical

waste burial areas (Site 1 and 2). The burial areas were covered with 13 cm of the chemical every third to fourth day. May
and September samplings at the landfill sites coincided with 1
month after the beginning and end of this application period.
Therefore, it is possible that the composition of the odorous gas
samples was affected by this application. However, the effect of
the chemical application is not significant on odor concentrations
since there was only a slight decrease at all sampling sites except
Site 5 that was possibly affected by the soil cover (Table 3).
VFA concentrations were very low and some of them could
not be detected in September in contrast to the fact that most of
them were found at all sampling sites in May (Fig. 1). The VFA
is a good indicator of waste decomposition process. Lower VFA
concentrations observed in September may be due to decreased
decomposition rate as a result of odor control chemical or due to
the sorption of the VFAs onto the alkaline chemical. However,
the decrease in other non-biogenic VOCs (i.e., monoaromatic
and halogenated compounds) concentrations in September
cannot be explained by the application of odor control chemical
since they are not end products of decomposition or they
are not likely to be sorbed by the chemical. The decrease in
concentrations of these VOCs was probably due to their lower
content in the wastes as a result of loss by evaporation during
a long and hot period.

Table 4
Pearson correlation coefficients between the different compound groups and odor (n = 10)

Odor
Total VOCs
Acids
Aldehydes
Esters
Halogenated compounds
Monoaromatics
Ketones
S and N compounds
*

Odor

Total VOCs

Acids

Aldehydes

Esters

Halogenated
compounds

Monoaromatics

Ketones

S and N
compounds

0.64*
1

0.23
0.63
1

0.91*
0.76*
0.21
1

0.52
0.87*
0.61
0.58
1

0.10
0.23
0.18
0.04
0.02
1

0.55
0.93*
0.69*
0.66*
0.94*
0.03
1

0.73*
0.88*
0.37
0.91*
0.79*
0.02
0.83*
1

0.41
0.02
0.33
0.53
0.30
0.03
0.18
0.29
1

Statistically significant (P < 0.05).

228

F. Dincer et al. / J. Chromatogr. A 1122 (2006) 222229

3.3. Relationship between the odor and total VOC

concentration
The characterization of VOCs at landfills [10] and odor
assessment on the basis of the dispersion of odors [1] were previously reported. However, previous studies did not investigate
the relationship between landfill odor and VOC concentrations.
The relationship between concentrations of odors and total
VOCs measured in the present study was analyzed statistically.
A correlation matrix was calculated for different variables and
Pearson coefficients were given as a measure of relationship
between groups of variables (Table 4). There are statistically
significant correlations (P < 0.05, n = 10) between odor concentrations and total VOC, aldehyde and ketone concentrations
(Table 4).
Linear regression analysis performed on the overall data set
(May + September) between odor and total VOC concentrations
indicated that 41% of the variance in odor concentrations can be
explained by the total VOC concentrations (r2 = 0.41, n = 10,
P < 0.05). The relationships of odor concentrations with the
concentrations of different groups of chemicals were further
examined using a step-wise multiple regression analysis. It was
found that the concentrations of aldehydes, ketones, and esters
are the best estimators, explaining 96% of the variability in odor
concentrations (r2 = 0.96, n = 10, P < 0.01).
4. Conclusions
The odor levels and the composition of odorous gases emitted from a municipal landfill site were studied. Up to 53 VOC
compounds in different classes (mono aromatics, halogenated
compounds, aldehydes, ketones, esters, and volatile fatty acids)
were identified and quantified.
The benzene-to-toluene ratio at the landfill site in May and
September was found to be significantly lower than the values determined in urban areas indicating the presence of higher
amounts of toluene than benzene in landfills compared to urban
areas.
Collected samples were also analyzed for odor concentrations by olfactometry. It is concluded that a relationship exists
between odor and total VOC concentrations at the studied landfill site. The relationships of odor concentrations with the different groups of chemicals were also examined and it was found
that the concentrations of aldehydes, ketones, and esters are the
best estimators, explaining 96% of the variability in odor concentrations.
Acknowledgement
This work was supported in part by the research fund of
Dokuz Eylul University (Project No. 03.KB.FEN.061) and
by the Scientific and Technical Research Council of Turkey
(TUBITAK) (Project No. ICTAG-A056). Olfactometric analyses were conducted in the laboratory established by the help
of the EU project; Odorous Emissions and Immissions Management Policy in Turkey-LIFE TCY/TR/000009. Authors are
thankful to panel members for their participation in olfactometry.

The help and permission by the Izmir Metropolitan Municipal Waste Management Authority should also be gratefully
acknowledged.

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