Water Research 36 (2002) 4023–4032

Characterization of humic substances present in landfill

leachates with different landfill ages and its implications
Ki-Hoon Kanga, Hyun Sang Shinb, Heekyung Parka,*
a
Department of Civil and Environmental Engineering, Korea Advanced Institute of Science & Technology, 373-1 Kusong Dong,
Yusung Gu, Taejon 305 701, South Korea
b
Department of Environmental Engineering, Seoul National University of Technology, Seoul 139-743, South Korea
Received 29 October 2001; received in revised form 2 March 2002; accepted 3 March 2002

Abstract

Humic and fulvic acids extracted from landfill leachates were characterized using elemental analysis and various
spectroscopic methods. Molecular size distribution of the humic substances (HS) was also determined using batch
ultrafiltration technique and permeation coefficient model. The element analysis and spectral features obtained from
UV/visible, IR, and 1H and 13C NMR showed that the aromatic character in the leachate HS was relatively lower than
that of commercial humic acid (Aldrich Co.), and higher in the HS of older landfill leachate. Fluorescence spectra
indicated that humic acids had a relatively higher content of condensed aromatic compounds than the fulvic acids
obtained from the same sources, and the spectrum of commercial humic acid showed that aromatic compounds may be
present in a much more condensed and complex form. Molecular size distribution data revealed that the leachate humic
acids contained a higher percentage of smaller molecules of o10,000 D, compared with that of the commercial humic
acid (45B49% vs. 33%), and molecular size of the leachate HS had a tendency to increase as landfill age increased.
These results indicate that the HS from landfill leachates were in an early stage of humification, and the degree of
humification increased as the landfilling age increased, which implies important information on various related
researches, such as interactions of HA with pollutants in terrestrial environments, and optimization of leachate
treatment processes with respect to landfill age. r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Humic substances; Landfill; Leachate

1. Introduction wastes, pesticides, etc. Because of this versatility, HS are

Humic substances (HS) are a naturally occurring
mixture of organic compounds, ubiquitous in nature,
which play an important role in both pollutant
chemistry and the biogeochemistry of natural waters
and soils [1]. One of the unique characteristics of HS is
its heterogeneity in terms of elemental composition,
chemical functionality, and molecular size distribution,
since HS can be derived from any organic materials,
including plant and animal debris, microfauna, bio-
*Corresponding author. Tel.: +82-42-869-3620; fax: +82-
42-869-3610.
E-mail address: hkpark@kaist.ac.kr (H. Park).
known to significantly affect the behavior of some
pollutants in natural environments, such as trace metal
speciation and toxicity [2–4], solubilization and adsorp-
tion of hydrophobic pollutants [5,6], disinfection by-
product formation [7], aqueous photochemistry [8,9],
mineral growth and dissolution, and redox behavior in
soils [10]. Recent studies have also suggested that HS
may be dynamically involved in carbon and electron
flow in anaerobic environments [11], which implies its
potential role in pollutant transformation, and, in some
cases, detoxification. These chemical features of HS
make it a promising candidate for pollution remedia-
tion. Furthermore, being an all-natural substance, it is
especially attractive for this use, because its own

0043-1354/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 3 - 1 3 5 4 ( 0 2 ) 0 0 1 1 4 - 8
4024 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032
pollution potential is minimal. From heavy metals
removal [12,13] to reductive dechlorination of chlori-
nated aliphatic hydrocarbons [14,15], photocatalytic
degradation [8,9], solubilization of hydrophobic organic
compounds [5,16], and oxidative coupling or binding
reactions [17,18] comprise these kinds of research using
HS or humic-metal complexes. However, the complex-
ities of the structural characterization of HS have posed
major challenges, which in turn have hampered a
molecular-level understanding of vital humic function-
ing in the environment.
In this study, an array of analyses was performed to
characterize HS extracted from several landfills with
different landfilling ages. Because of the number and size
of landfills and the long time periods of a potential risk,
groundwater contaminated by leachate from unsanitary
or even inappropriately designed or constructed sanitary
landfill has posed serious problems in water resource
conservation, and may make some of the traditional
remediation technologies (e.g., excavation, pump and
treat, and perhaps capping) less cost effective [19,20].
Therefore, knowledge about the roles and interactions
of HS as well as its characteristics is essential to evaluate
the risk of pollution and to establish optimal remedia-
tion strategy. The results of this study may provide basic
information for the understanding of the changes in
aquifer environments contaminated by landfill leachate
and interactions of pollutants with HS.
2. Materials and methods
2.1. Landfill leachates
Leachates were collected from three landfills, located
in Korea, with different landfilling ages to analyze
differences in the characteristics of HS with landfilling
age; young landfill with landfilling age of o5 years
(landfill-G), medium-aged landfill of 5–10 years (landfill-
P), and old landfill of more than 10 years (landfill-N).
Landfill-G is a sanitary canyon/depression landfill and
has been operated since August 1996, mainly for
municipal wastes. Landfill-P is also a sanitary landfill
constructed on reclaimed seashore land. It has been
operated since February 1992, mainly for municipal
wastes. Landfill-N is a closed unsanitary landfill, and
stabilization construction is currently underway. Mainly
municipal wastes with construction wastes, sewer sludge,
and some industrial wastes were landfilled for 15 years
(March 1978–March 1993). Leachate of this landfill was
collected from the slope of the landfill since there was no
leachate collection system at the time of sampling due to
the stabilization construction. All the leachates were
collected between August 13 and 17, 1999, which
showed the typical Korean summer climatic conditions
of high temperature and humidity after a rainy spell
from the end of July to the beginning of August. Water
quality of the leachates was analyzed.
2.2. Extraction of humic substances
Extraction of HS from the leachates was performed
by acid–base treatment method proposed by Thurman
and Malcolm [21]. Amberlite XAD-7 resin (specific
(
surface area: 450 m2/g, average pore diameter: 90 A,
particle size: 20–60 mesh) purchased from Sigma
Chemical Co. (Milwaukee, WI) was used for the
extraction after cleaning with 0.1 N NaOH for 5 days
to remove impurities and Soxhlet-extracting sequentially
for 24 h with methanol, diethyl ether, acetonitrile, and
methanol.
The leachate samples were centrifuged and filtered
through glass-fiber filter paper (0.45 mm) to remove
suspended materials that may react with HS. The
extracted HS were separated into humic and fulvic
acid fractions by acidifying the HS solution to
pH 1.0 and precipitating humic acid fraction. Both
fractions were then passed through a strong cation
exchange resin (DOWEX 50WX8-100, Aldrich Chemi-
cal Co.) in the hydrogen-saturated form. Finally, the
hydrogen-saturated acids were lyophilized for further
analyses.
2.3. Analysis of humic substances
The elemental composition of the humic and fulvic
acids was determined with Element Analyzer (EA1110-
FISONS). Various spectroscopic methods have been
used to obtain segmentary information on the structure
of humic and fulvic acids [22]. UV–visible absorption
spectra of the humic and fulvic acids were recorded on
Beckman spectrophotometer (DU70), using 10 mm
quartz cell. 100 mg/L of fresh HA and FA solutions
were prepared with pH adjusted to 6.0. Spectra of the
solutions were obtained over a wavelength range of
300–800 nm. Absorbance at 280, 465, and 665 nm were
also measured. These solutions were also used to record
fluorescence spectra on a AMINCO Bowman series 2
Luminescence spectrometer in both excitation and
emission scanning modes. Infrared spectra were re-
corded with KBr pellet (100 mg KBr+1 mg sample) on a
BOMEM MB154 FT/IR Spectrometer.
For nuclear magnetic resonance (NMR) spectra,
solutions were prepared by dissolving 50 mg of each
sample in 1 mL of 1.0 N NaOD (in D2O). 1H and 13C
NMR spectra were recorded at 300 and 75.47 MHz,
respectively, with Bruker DRX300 NMR. Inverse-gated
decoupling was used under the condition of 0.2 s
acquisition time and 2.0 s interpulse delay at 451 pulse
width, to minimize distortions due to the nuclear
Overhauser enhancement (nOe) effect on different
 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032 4025

carbon types and lack of complete relaxation of all
carbons.
Molecular weight distribution of the HS was analyzed
by batch ultrafiltration (UF) methods. All UF experi-
ments were performed at room temperature in 200 mL
stirred cell (Amicon Co., Model 8010, Danvers, MA)
pressurized to 50 psi using nitrogen gas. The types
and nominal molecular weight cutoffs (MWCOs) of
the membranes, as specified by the manufacturer
were: YM1=1000 D (1k); YM10=10,000 D (10k);
XM50=50,000 D (50k); and YM100=100,000 D
(100k). UF was performed with parallel processing
mode for each MWCO using 100 mL of sample. The
concentrations of the filtered samples collected through
fraction collector (Pharmacia, Uppsala, Sweden) were
measured by UV absorbance (DU70, Beckman) at
280 nm. Batch UF data were applied to a two-parameter
nonlinear permeation coefficient model (PCM) pro-
posed by Logan and Jian [23] to account for the
phenomenon of retarded solute transport due to
membrane–solute interactions. The PCM, derived from
a solute mass balance around a pressurized batch UF
cell, is mathematically expressed as
Cp ¼ pCr0 F p
1 ;
where Cp is the instantaneous solute concentration in
membrane permeate, Cr0 is the actual solute concentra-
tion in the sample nominally sized to pass the
membrane, p is defined as the permeation coefficient,
and F is the instantaneous fractional reduction in
retentate volume ðF ¼ 1
ðVp =V0 ÞÞ: PCM parameter
estimates (p and Cr0 ) are determined by using linear
regression to fit batch UF data (ln Cp vs. ln F ) using the
linearized form of Eq (1):
ln Cp ¼ ln ðpCr0 Þ þ ðp
1Þ ln F : ð2Þ
All the analyses were performed with humic acid
purchased from Aldrich Chemical Co. (Lot No.
11909LR) as a reference material.
3. Results and discussion
3.1. Water quality of the leachates
From the results of water quality analysis, it was
found that the leachates possessed typical characteristics
with landfilling age (Table 1); that is, pH was increased
as landfilling age increased, while organic concentration
(measured as COD, BOD, and DOC) was decreased.
The TBOD to TCOD ratio was significantly reduced
from 0.79 of Landfill-G to 0.11 of Landfill-N, which
represents the decrease in biodegradability of the
leachates with respect to their age. TCOD of Landfill-
ð1Þ G was extraordinarily high (41,507 mg/L), which may
have been due to the sampling time which followed a
rainy spell and 2 weeks of continuous high temperature.
Furthermore, the type of the landfill (canyon/depres-
sion) may have caused a rapid effluence of leachate by
the precipitate. ORP of Landfill-N was also extraordi-
narily high, which may have been due to the sampling
point on the landfill slope. Very high concentrations of
volatile fatty acids of Landfill-G indicate its acid phase,

Table 1
Some of the results of water quality analysis for the three leachate samples

Parameter Landfill-G Landfill-P Landfill-N Parameter Landfill-G Landfill-P Landfill-N

Organics (mg/L) Volatile fatty acids (mg/L)

TCOD 41,507 5348 1367 Acetic acid 5861 187 NDb

SCOD 38,969 4749 1106 Propionic acid 1959 368 NDb
TBOD 32,790 2684 145 n-Butyric acid 4001 824 NDb
SBOD 29,990 2195 138 Iso-butyric acid 504 131 NDb
TBOD/TCOD 0.79 0.50 0.11 n-Valeric acid 2237 80 NDb
DOC 18,362 1630 863 Iso-valeric acid 428 53 NDb
n-Caproic acid 2217 19 NDb

Solids (mg/L) Miscellaneous

TS 32,685 13,095 4815 pH 6.6 7.9 8.2

TVS 17,956 3587 907 ORP (mV)
208
490 14.9
SS 1873 143 17.2 TKNa 2482 2192 1064
VSS 1367 86.7 7.0 NH+4 -N
a
1896 1826 892
Alkalinitya 9130 7928 2784
a
mg/L.
b
Not detected.
4026 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032

Table 2
Elemental composition (normalized to 100% of organic components) and ratios of leachate HS

Elements /ratios Humic acids Fulvic acids

a
G P N AHA Literature G P N Literaturea

Aquatic Terrestrial Aquatic Terrestrial

C 56.2 57.1 56.1 50.3 53–60 54–62 45.6 53.6 50.9 42–51 43–53
H 8.8 7.0 7.2 5.7 3.7–5.1 2.9–5.8 9.6 6.7 6.4 3.6–4.3 3.3–5.9
O 26.7 30.2 29.3 43.6 33.4–40.8 29.5–36.8 32.8 33.8 35.2 44.2–53.2 42.9–51.4
N 8.3 5.7 7.4 0.4 2.0–2.1 1.6–4.8 12.0 2.5 2.4 1.0–1.6 0.7–4.1
S NDb NDb NDb NDb — — NDb 3.4 5.1 — —

H/C 1.54 1.48 1.88 1.35 0.74–1.15 0.56–1.29 1.51 1.49 2.53 0.85–1.23 0.75–1.65
O/C 0.39 0.40 0.36 0.65 0.42–0.58 0.36–0.51 0.52 0.47 0.54 0.65–0.95 0.61–0.90
N/C 0.11 0.09 0.13 0.01 0.029—0.034 0.022—0.076 0.04 0.04 0.23 0.017—0.033 0.011—0.082
a
[24,25].
b
Not detected.

while any volatile fatty acids were not detected from the 2.0

leachate of landfill-N.
a - Aldrich HA
b - N-HA
3.2. Chemical and spectroscopic characteristics of the 1.5
c - P-HA
humic substances
Absorbance

d - G-HA
1.0 e - N-FA
The results of element analysis for leachate HS,
f - P-FA
normalized to 100 wt% of organic components, are
g - G-FA
shown in Table 2 together with the average values of a
0.5 b
aquatic and terrestrial HS given in literature [24]. c
Although it is difficult to infer a general trend of the d
e f
compositional characteristics, the HS extracted from the g
0.0
leachates have a higher content of carbon and hydrogen, 300 400 500 600 700 800
and a lower content of oxygen than those of AHA and Wavelength (nm)
the literature. The high concentration of nitrogen in
leachate HS may be caused by the high ammonia-N Fig. 1. UV–visible spectra of humic and fulvic acids (100 mg/L
concentrations of leachates. at pH 6.0).
To obtain more detailed information on the HS,
atomic ratios of H/C, O/C and N/C were calculated process proceeds [26], become higher in AHA than the
from the element analysis results. Typically the H/C leachate HS, and also higher in the HS with older
ratios are clustered around 1.0, which implies a chemical landfilling age.
structure consisting predominantly of aromatic frame- To investigate these characteristics in detail, absorp-
work [25]. Therefore, the relatively high H/C ratios in tion coefficient at 280 nm (e280 ) and ratio of absorption
the leachate HS imply that the structures contain coefficients at 465 and 665 nm (e4 =e6 ) were measured
significant portions of aliphatic functional groups. On (Table 3). The values of e280 ; which is used as an
the other hand, O/C ratios were relatively lower than indicator for the aromaticity of a sample’s structure [27],
those found in literatures [24,25], which means lower were lower in the leachate HS than that of AHA, and
contents of oxygen-possessing carbohydrate. showed an increasing trend with landfilling age. This
The UV–visible spectra of the leachate HS are shown means that the aromaticity of the leachate HS is
in Fig. 1. The leachate HS generally gave lower relatively low and increases with landfilling age. The
absorbance than AHA in the spectral range. Both values of e4 =e6 ; which are generally known to be
humic and fulvic acids from Landfill-N and P have inversely proportional to molecular weight and propor-
similar absorption intensities, which are, on the other tional to acidity, were higher than that of AHA, but
hand, significantly higher than those from Landfill-G. showed no trend with landfilling age.
This may suggest that the aromaticity and molecular Fig. 2 is the FT/IR spectra of the HS that give
weight, which are known to increase as humification information about specific molecular structures and
 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032 4027

Table 3
Absorption coefficients of the humic and fulvic acids (100 mg/L at pH 6.0)

Parameter Humic acids Fulvic acids

Landfill-N Landfill-P Landfill-G Aldrich Landfill-N Landfill-P Landfill-G

a
e280 12.6 11.4 3.0 20.8 8.4 7.3 0.8
e4 =e6 5.52 6.50 5.10 4.16 6.52 6.88 5.46
a
L/g cm.

-1
1700 cm 1630 cm-1

Aldrich HA

Landfill G - HA
Absorbance

Landfill P - HA

Landfill N - HA

Landfill P - FA Landfill G - FA

Landfill N - FA

4000 3000 2000 1000

-1
Wavenumber (cm )
Fig. 2. FT/IR spectra of humic and fulvic acids.

various functional groups [28]. All spectra have typical
bands of common soil and aquatic HS; 3400 cm
1
(H-bonded OH), 2900 cm
1(aliphatic C–H stretching),
1690–1710 cm
1(C ¼ O stretching of COOH and ketonic
C ¼ O), 1540 cm
1(C ¼ N stretching, amide II band),
1240 cm
1(C–O stretching) [29]. Therefore, it can be
concluded that the characteristics of functional groups
of both leachate HS and AHA molecules were basically
similar. However, the strengths of the bands, which give
differences of the relative distribution of each functional
group, have some differences. Leachate fulvic acids have
relatively stronger absorption bands at 1690–1710 cm
1,
while having lower absorption bands at 1630 cm
1,
which is attributed to the peak by carbon double bonds
in benzene rings. These results indicate that leachate
fulvic acids may have higher acidity than humic acids.
AHA also showed higher absorption band at 1630 cm
1
than leachate HS, which means AHA was more
aromatic than leachate HS, and these results agree with
those from element analysis.
Fluorescence spectra of the HS in excitation and
emission scanning modes (Fig. 3) were recorded to
obtain more detailed information about the condensed
aromatic structures in humic and fulvic acids [30]. All
the humic and fulvic acids have similar fluorescence
characteristics in excitation mode (Fig. 3a) that show
maximum peaks at 360 and 400 nm. The fluorescence
intensity of AHA is lower than those of humic acids
from landfill-P and N, and this is contradictory to the
results obtained by other analyses, such as element
analysis and UV–visible spectrophotometry. The possi-
ble reason may be explained from the completely
different sources (probably coal-based) and relatively
high amount of impurities (usually 20–30%) of the
commercial humic acid. Based on the available data of
fluorescence properties of various fluorophores [31], the
shorter wavelength peaks (360 nm) can be interpreted to
be mainly due to the presence of simple aromatic rings in
the molecules, while the peaks at the longer wavelength
region (400 nm) may be due to fluorophores of the
condensed aromatic rings and conjugation of simple
aromatic rings. The ratio of intensities of the peaks of
400 nm to the peaks of 360 nm in humic acids is
relatively higher than those of fulvic acids. These results
4028 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032

10 molecular size of the leachate HS with landfilling age,

(a)
which, in turn, caused decrease in spin–spin relaxation
8
time (T2 ) due to the slow molecular rotation of large
P-HA molecules in the solutions. For a more effective
comparison, each spectrum was quantitatively analyzed
Fluorescence

6
N-HA on the basis of Preston [32], and the results are presented
in Table 4. Leachate HS showed relatively higher
4 AHA percentages (62.9–73.5%) of protons on aliphatic
carbons (regions I and II) than that of AHA (47.0%).
N-FA
2
The percentages of proton on a-carbon to oxygen
P-FA G-HA function or carbohydrates (region III) in the leachate
G-FA HS accounted for 17.2–23.0%, as compared to 16.6% in
0
300 350 400 450 500
AHA.
On the whole, the percentages of aromatic protons
Wavelength (nm)
(region IV) of the leachate HS were very low
10
(6.9–14.4%), compared to that of AHA (36.4%). The
(b)
P-HA
results show that the molecules of leachate HS contain
8 larger proton of aliphatic components than that of
N-HA
AHA, which is consistent with the results obtained from
Fluorescence

6
G-HA
4
N-FA
AHA
2 the relatively high distribution of amino acid carbon
P-FA
G-FA
0
400 420 440 460 480
Wavelength (nm)
Fig. 3. Fluorescence spectra of humic and fulvic acids in: (a)
excitation, and (b) emission scanning modes.
may suggest that aromatic components in humic acid
molecules are present in the form of higher condensed
aromatic rings than those in fulvic acids. The fluores-
cence spectrum of AHA has relatively strong intensities
in the region >400 nm than those of any other leachate
HS. This means Aha molecules contain more condensed
aromatic rings of complex form. Generally, as landfilling
age increases, fluorescence intensity increases, although
the spectra of humic acids of Landfill-N and P were
very similar. These results agree well with those from
UV–visible spectroscopy. Fluorescence spectra in the
emission mode (Fig. 3b) showed the same trend as that
in excitation mode.
1
H NMR spectra were obtained for basic structural
information of the HS (Fig. 4). Peak characteristics of
all the spectra are very similar; that is, all spectra consist
of wide peaks in the region of 6.0–8.0 ppm (aromatic H),
strong peaks at 3.6 ppm (carbohydrate H), and char-
acteristic peaks at 2.1, 1.2, and 0.9 ppm (aromatic CH2,
CH3). As landfilling age increased, most of the peak
signals of leachate HS became broader. This decline of
spectra resolution may be caused by an increase in
the IR spectra and elemental analysis.
13
C NMR spectra were also quantitatively analyzed,
and the distributions are presented in Table 5. The
relatively high nitrogen content of the leachate HS (from
water quality and element analysis) may contribute to
(50–60 ppm) in region II. The percentages of aromatic
carbon of leachate HS accounted for 26.2–36.2%, which
500 520 540 560 were similar or relatively lower than that of AHA. The
intensities of region I became higher in the leachate HS
from the older landfill of Landfill-N and Landfill-P
(21.6–27.4%) than that of younger landfill of Landfill-G
(14.6–19.6%). This may result from the decomposition
steps of landfill waste from the acid to methanogenic
phase. This characteristic can also be judged by the
lower content of region II, which is attributed to alcohol
and acetyl groups, in the leachate HS of older landfill.
3.3. Molecular size distribution by permeation coefficient
model
Knowledge about the distribution of molecular size
fractions is very important for understanding the basic
chemistry of HS. It has been shown that the chemical
characteristics and interaction behavior with hydropho-
bic organic pollutants and metal ions significantly differ
with respect to molecular size of HS [4,33]. Fig. 5 shows
the results of molecular weight distribution analysis for
the leachate HS and AHA by applying batch UF data to
PCM. A major part of the molecules of the leachate
humic acids and AHA were distributed in the region of
10k to 100k. AHA contained 77% of the molecules in
this region, while the leachate humic acids contained 61–
65%. AHA also contained 16% of its molecules in a
high molecular weight region (>100k), while only
3–12% of the leachate humic acids were distributed in
this region. On the other hand, the distribution of the
 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032 4029

Fig. 4. 1H NMR spectra of: (a) humic, and (b) fulvic acids.

Table 4
1
H chemical shift regions and their relative contributions of the leachate humic and fulvic acids

Chemical shift Assignment Relative contributions (%)

region d (ppm)
Humic acids Fulvic acids

N P G Aldrich N P G

I (0.4–1.7) Terminal CH3, and CH2, CH of methylene 36.9 45.0 38.1 19.1 40.8 41.1 41.2
chains, etc.
II (1.7–3.3) CH3, and CH2, CH proton a to aromatic 26.0 28.3 28.4 27.9 28.5 32.4 29.0
or carboxyl groups, etc.
III (3.3–4.6) Protons on carbon a to oxygen, 23.0 17.2 19.1 16.6 18.8 19.6 21.7
carbohydrates, etc.
IV (6.5–8.1) Aromatic protons (including quinone, 14.1 9.5 14.4 36.4 11.9 6.9 8.1
phenol, etc.)

Table 5
13
C chemical shift regions and their relative contributions of the leachate humic and fulvic acids

Chemical shift Assignment Relative contributions (%)

region d (ppm)
Humic acids Fulvic acids

N P G Aldrich N P G

I (0–50) Alkyl carbons 21.6 27.4 14.8 12.5 25.2 26.2 19.6
II (50–110) Acetyl and CO carbons 28.5 20.0 38.0 18.9 25.5 19.1 38.3
III (110–160) Aromatic carbons 30.9 36.2 26.2 34.2 29.9 27.2 27.3
IV (160–200) Carboxyl carbons, carbons in aldehydes, 19.0 16.4 21.0 34.4 19.4 27.5 14.8
ketones, C=S groups

leachate humic acids in the low molecular weight region molecular size of the leachate humic acids were smaller
(smaller than 1k) comprised 15–19%, while AHA than that of AHA, and, as a result, the degree of
contained o1%. These overall results indicate that the humification of the leachate humic acids was lower.
4030 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032
Fig. 5. Results of the molecular weight distributions of: (a) humic, and (b) fulvic acids extracted from landfill leachates with respect to
landfilling age.
On comparing the distribution characteristics of each
leachate humic acid, the major part (76%) of Landfill-N
humic acid was distributed in a molecular weight region
>10k, that of Landfill-P humic acid in 1k–100k (78%),
and that of Landfill-G in a region under 50k (79%). As a
result, although the trend of molecular weight distribu-
tion characteristics was not clear, the distribution of
molecular weight of the leachate humic acids moved into
higher molecular weight as the landfilling age increased.
In the case of fulvic acid, the distribution of o50k for
all the cases was 91–94%, while that of the humic acids
was 49–79%. This means that the molecular weight of
the fulvic acids was much smaller than that of the humic
acids, which suggests fulvic acid could have a more
important role in the mobility of pollutants in the
environment [34]. On comparing the distribution of the
leachate fulvic acids with molecular weight below 10k,
the proportion of the molecular weight increased with
decreasing landfilling age, 59% in Landfill-N, 63% in
Landfill-P, and 74% in Landfill-G. Therefore, the
distribution characteristics of the leachate fulvic acids
with landfilling age was somewhat clearer than in the
case of humic acids.
Based on the results, it can be suggested that the
distribution of the molecular weight of the leachate HS
moved towards higher molecular weight as landfilling
age increased, with some ambiguity. This may result
from the fact that the characteristics of the leachate
produced in landfill depends on the composition of
landfilled wastes, landfill method, type of leachate
collection system, and local weather conditions as well
as the landfilling age.
4. Conclusions
In this work, we have extracted humic and fulvic acids
from three landfills with different landfilling ages, and
conducted chemical and spectroscopic characterization
of the HS with commercial humic acid (Aldrich Co.) as a
reference material. We have identified certain differences
between the leachate HS and the commercial humic
acid, and among the leachate humic and fulvic acids
with different landfilling ages. One such difference was
that leachate HS were comprised of molecules of
smaller size and less aromatic in nature compared to
those of the commercial humic acid. We have also
observed that the aromatic ring in molecules of leachate
HS was less condensed than that of the commercial
humic acid. Such differences in the molecular size and
structural characteristics suggest that the leachate HS
were in a lower degree of humification than commercial
humic acid, and they affect their solubility and the
migrational behavior of some pollutants in natural
systems. Another difference was in the leachate HS with
different landfilling age, in which the aromatic compo-
nents and molecular size of the HS increased with
increasing landfilling age. These results suggest that the
degree of humification increased as the landfilling age
increased.
There are various researches currently being per-
formed on HS as an agent especially for groundwater
remediation. Furthermore, application of HS in the
wastewater treatment has also been considered,
although there are still some limitations in the applica-
tion. The interaction of HS (aquatic as well as soil-
bound) with many refractory organic compounds, which
is important in the understanding of natural attenuation
processes in terrestrial system and, in turn, can be
applied as a remediation method, will be significantly
affected by the characteristics of HS, such as aromati-
city, molecular weight, acidity, functional groups, etc.
The information on the characteristics of HS present in
landfill leachate results with respect to landfill age,
therefore, can be referred in various related fields of
research, such as optimization of leachate treatment
 K.-H. Kang et al. / Water Research 36 (2002) 4023–4032
processes and leachate-contaminated groundwater re-
mediation.
Acknowledgements
This work was supported by the Brain Korea 21
Project.
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