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Science of the Total Environment 361 (2006) 25 37

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Characteristics of landfill leachates in central Taiwan


Huan-jung Fan *, Hung-Yee Shu, Hsin-Sin Yang, Wen-Ching Chen
Department of Environmental Engineering, Hungkuang University No. 34, Chung-Chie Rd, Sha-Lu, Taichung, 433 Taiwan, ROC
Received 23 September 2004; received in revised form 18 August 2005; accepted 10 September 2005
Available online 2 December 2005

Abstract
Due to the complex nature of landfill leachates, the leachate treatment plants have difficulty to meet the current Taiwan EPAs
effluent standards. Three typical types of landfills, closed landfill A, mixed landfill B (disposal of MSW with bottom ashes from
MSW incinerators) and direct MSW landfill C, (disposal of MSW only), are investigated in this research in order to have a better
understanding of characteristics of leachates. Factors investigated in this research include landfill age, pH, BOD, COD, TS, DS,
VS, seasons, metals (Pb, Ca, Cd, Hg, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, and Zn), humic substances (humic acid, fulvic acid, and nonhumic substance), aromaticity and toxicity. Results show that the active landfills B and C had the significant higher concentration
of COD, VSS, TS, PtCo, TOC and conductivity. The mixed landfill B had the higher DS, TS, Na, Ca, Mg and conductivity than
that of direct MSW landfill C. Direct MSW landfill C had the highest contents of Fe, Cr, Ni and acute toxicity among these
landfills. A significant degree of variation was encountered and factors which may influence leachate quality were identified and
discussed.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Landfill leachate; Temporal variation; Humic acid; Metal; Toxicity

1. Introduction
The municipal solid waste (MSW) has been a major
environmental problem in Taiwan. The MSW generated
in Taiwan has reached 7 million tons per year. Traditionally, most of the municipal solid wastes (MSW)
were disposed directly into sanitary or simple landfills
in Taiwan. However, in recent years, due to the difficulty of finding new locations for landfills, the MSW
treatment policy of Taiwans EPA was moved toward
incineration of MSW to extend the usage time of landfills. For example, the percentage of incineration of
MSW increased rapidly from 50% to 70% for the past
* Corresponding author. Tel.: +886 4 26318652; fax: +886 4
26525245.
E-mail address: fan@sunrise.hk.edu.tw (H. Fan).
0048-9697/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2005.09.033

three years as shown in Fig. 1. Currently, there are 20


major MSW incinerators and more than 300 small scale
industrial incinerators in Taiwan. The MSW produced
from metropolitan areas (mostly in west coast of Taiwan) was incinerated before landfilling; on the other
hand, most of the remote and rural areas of Taiwan are
still using the sanitary and simple landfills for the
disposal of MSW. Sanitary and simple landfills were
landfills with and without proper leachate collecting
facilities, respectively. Due to the increasing percentage
of incineration of MSW, the number of Taiwans landfills was a graduating switch from directly MSW landfills to mixed landfills (including MSW with bottom
ash produced from MSW incinerators). Therefore, there
is a need for understanding the properties of leachates
generated from mixed landfills for the proper treatment
of leachates, especially in central Taiwan.

26

H. Fan et al. / Science of the Total Environment 361 (2006) 2537


Incineration
Sanitary landfill
Simple landfill

100

Percentage(%)

80

60

40

20

0
2001

2002

ing from direct MSW landfilling to mixed landfilling


(MSW and bottom ashes) for the past few years and the
basic information of the landfill leachate in Taiwan was
very insufficient (Chen, 1996). As groundwater and
surface water pollution are concerned, leachate quality
deserved a careful scrutiny and analysis to prevent
further damage to the environment (Koerner and
Soong, 2000). Therefore, it is essential to understand
the characteristics of various types of landfill leachates
for the proper treatment of the leachates. This study
focuses on the three typical types of landfills: closed
landfill A, mixed landfill B and direct landfill C located
in central Taiwan.

2003

Year

2. Methods

Fig. 1. The MSW treatment methods in Taiwan (Taiwan EPA, 2003).

2.1. Landfill sampling sites


The leachate takes up organic and inorganic constituents by means of physical, hydrolytic and fermentative processes, thus, it contains a high concentration of
organic matters and inorganic ions, including heavy
metals (Robinson et al., 1982; Tchbanoglous et al.,
1993). As pointed by numerous researchers, leachate
is a serious environmental problem to discharge heavy
metals continuously, if it is not handled properly (Sletten et al., 1995; Urase et al., 1997; Christensen et al.,
1998; Fytianos et al., 1998; Chen et al., 1998; Poon and
Chen, 1999; Abu-Rukah and Al-Kofahi, 2001). The
presence of humic substance in leachate might enhance
the transportation of heavy metals. Furthermore, the
increase of ash content in landfill may increase the
heavy metal and salts concentrations in leachate
(Urase et al., 1997).
Effluents from municipal solid waste landfills have
to comply with Taiwans environmental regulations
such as COD b 200 mg L 1. Currently, the biological
processes (aerobic or anaerobic) are the most commonly used methods in the MSW leachate treatment processes in Taiwan. However, most of the treatment plants
have difficulty to meet this effluent standard due to the
complex nature of the leachate. One of the main reasons
was the landfill leachate has been changing due to the
disposal of MSW into landfills, which has been switch-

One closed landfill A and two active landfill sites B


and C in central Taiwan had been selected for investigation of leachate properties due to their characteristics
and comparative advantage. The characteristics of the
three sites are listed in Table 1. The site A, located in
Taichung city, received mainly municipal solid wastes.
This site was in operation from 1988 to 1994. Therefore, the leachate originates from landfill ranging between 1117 years old. Sites B and C are typical
landfills for urban and rural areas in Taiwan, respectively. Site B is located in the city as well and has been
accepting municipal solid waste for approximately 10
years. Site B covers about 240,000 m2 with total capacity of 3,400,000 m3. This site receives both collected MSW and incineration ash from MSW incinerator.
The composition of received waste in site B are MSW
(20%60%) and incinerator bottom ashes (40%80%).
Site C is located at rural area of central Taiwan and
receives mainly rural municipal solid wastes with landfill age around 12 years. The site C is a typical rural
area landfill in Taiwan.
2.2. Sampling procedure and analytic methods
Landfill leachate samples were collected and maintained under conditions with minimized exposure to

Table 1
Characteristics of landfills
Site

Location

Status

Operation since

Landfill age (yr)

Waste compositions

A
B

Urban
Urban

Closed
Active

19881994
1995

1117
10

Rural

Active

1993

12

MSW
MSW (20%60%)
Bottom ashes (40%80%)
MSW

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

oxygen. Leachates were collected monthly from February 2001 through July 2003. In the laboratory, leachate was filtered through a 0.2 um membrane and stored
at 4 8C in the dark.
The parameters analyzed in this research include pH,
SS (suspended solid), VSS (volatile suspended solids),
TS (total solid), TOC (total organic carbon), COD
(chemical oxygen demand), BOD (biological oxygen
demand), metals (Pb, Ca, Cd, Hg, Cr, Cu, Fe, K, Mg,
Mn, Na, Ni, and Zn), and humic substances (humic
acid, fulvic acid, and non-humic substance).
Humic acid, fulvic acid and non-humic substance
were extracted from landfill leachate through resin
XAD8. The procedure used for separation and purification of humic and fulvic acid was based on the
method described by Christensen et al. (1998) and
Thurman and Malcolm (1981).
The leachates were freeze-dried (Freeze Dryer FD81, Eyela Tokyo Rikakiai Co. LTD) and then analyzed
by Elementar Elemental Analyzer (Vario EL) for contents of carbon, hydrogen, oxygen, nitrogen and sulfur.
Freeze-dried samples of leachate were analyzed from
4000 to 600 cm 1 using a Fourier-Transform Infrared
Spectrometer (Bomem, A8.3, CA).
Acute toxicity of leachate was tested by Microtox
Model 500 Analyzer. The leachate pH was maintained
between 6 and 8 and was filtered through 0.45 Am filter
(Cellulose nitrate, Micro Filtration System, Dublin,
CA) before it was analyzed.
3. Results and discussion
3.1. Waste management in Taiwan
Currently, there are more than 300 landfills (55%
active sanitary landfills, 25% active simple landfills and
19% closed landfills) and 21 major incinerators in
Taiwan (Taiwan EPA, 2003). Most of the landfills are
located in west coast of Taiwan where population is
concentrated. Details of the locations of these landfills
are listed in Fig. 2. In Taiwan, since more than 30% of
water are obtained from groundwater reservoirs, serious
environmental consequences such as soil and groundwater contamination might result from improper handling of these landfill leachates, especially that some of
the landfills are located in the water resource preservation areas in Taiwan. Therefore, it is vital to further
understand the characteristics of landfill leachate for the
proper treatment of the leachate. This study selected
three typical types of landfills located in central Taiwan.
Landfill sites A, B and C are typical cases of closed
landfill, mixed landfill (MSW and bottom ash) and

27

direct MSW landfill sites respectively in Taiwan. The


color of leachates from landfills B and C appeared as
thick dark color, while leachate from site A had a light
brown color.
3.2. Chemical characteristics of leachates
Chemical characteristics of the leachate samples are
analyzed and summarized in Table 2. Scheffes tests
( P = 0.05) were conducted using SPSS (2000) to test
the statistics significance among these sites (SPSS,
2000). As shown in Table 2, mean pH values of
leachates were between 7.74 and 7.91 with no statistic
significant difference among these sites. The mean
concentrations of COD of landfills A, B, and C
were about 690, 2483, and 3038 mg L 1, respectively
(Table 2). Mean COD concentrations of active landfill
sites B and C were statistically higher than that of
landfill A. Although landfill C had a higher mean
COD concentration (3038 mg L 1) than landfill B
(2483 mg L 1), this value had not reached statistically
significant level. As shown in Table 2, similar findings
were observed for BOD (biological oxygen demand),
TOC (total organic carbon), VSS (volatile suspended
solid) and color. This result indicated that the organic
contents in closed landfill A were significantly lesser
than active landfills B and C. The mixed landfill B
had lower organic contents than that of landfill C.
However, the organic content difference between landfills B and C did not reach statistically significant
level. It might due to the high concentration variation
of these organic contents.
The average concentrations of TS of leachates for
landfills A, B, and C were 3941, 9620, and 6787 mg
L 1, respectively. Statistically speaking, the sequence of
TS was B N C N A. Similar sequences were observed for
DS and conductivity as well. Landfill B had much higher
contents of DS, TS and conductivity than landfill C. This
result indicated that mixed landfilling would increase
DS, TS and conductivity in leachate which might be due
to the disposal of bottom ashes of incinerators.
The experiment showed that chemical composition
of leachate varied significantly over time. For example,
as indicated in Fig. 3a, the range of COD in landfill B
was from 500 to 4500 mg L 1. Similar results were
obtained for SS contents as well (Fig. 3b). This result
indicated that it is not appropriate to take only one or a
few samples of leachates to represent the average contents of leachates, because the chemical contents of the
leachate might be easily over- or under-predicted.
Therefore, it is essential to conduct a long-term monitoring program to obtain representative information of

28

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

Taoyuan

Taipei

Hsinch
Yilanu

Miaoli

Taichung

Changhua
Penghu

Nantou
Yunlin

Hualien

Chiayi
Tainan

Kaohsiung
Taitung

Pingtung

Fig. 2. Location of sanitary landfills (D), simple landfills (5) and major incenirators in (o) Taiwan (Taiwan EPA, 2003).

leachate. In addition, the property of fluctuation of


leachates might further complicate the removal efficiency of treatment processes. This fluctuation should be
considered when operating the leachate treatment plant.
The chemical contents of leachates studied in this
research had been compared with landfills in Hong
Kong, Kuwait, USA and Germany as shown in Table
3 (Chu, 1994; Al-Yaqout and Hamdoa, 2003). The
leachates generated from active landfill sites B and C
had higher organic contents COD than those of Hong
Kong (JB and GDB) but lower than those of Kuwait,
USA and Germany. This is evident that the characteristics of local leachate should be studied for the proper
treatment of leachate. The leachate from USA landfills
had a relatively lower pH value than other countries,
which might be due to its young landfill age. The BOD

values of sites B and C were significantly lower than


those of Kuwait, USA and Germany. Once again, this
result indicated that the biological treatment methods
might not be suitable for these landfills in Taiwan.
3.2.1. BOD / COD and COD / TOC
Fig. 4 illustrates the relationship between COD and
BOD and shows the different patterns among these
three typical types of landfills. For example, most of
the COD and BOD contents of site A were less than
1200 and 100 mg L 1, respectively. The site B
appears to have a linear relationship between BOD
and COD with slop of 1 / 16 while the BOD contents
were less than 250 mg L 1. Most of the COD contents of site C were clustered around 30004000 mg
L 1 with only two exceptions regardless the BOD

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

29

Table 2
Chemical characteristics of leachate at various landfills
Parameters (mg L

1 a

pH
COD
VSS
PtCo color
TOC
SS
BOD
DS
TS
Conductivity
BOD / COD
COD / TOC
a
b
c

Site A

Site B

Site C

Mean

SD

Mean

SD

Mean

SD

Scheffes testb

7.74
689.6
51.1
1781.6
248.8
33.9
49.6
3906.9
3940.9
8571.8
0.06
2.99

0.38
327.1
74.0
631.4
109.3
18.3
29.8
1337.8
1343.2
2883.4
0.07
1.64

7.91
2483.3
165.8
5513.4
867.3
155.9
164.6
9463.6
9619.5
23753.8
0.06
2.82

0.26
1046.7
116.2
1860.9
403.5
71.3
132.0
2638.5
2630.6
7249.3
0.03
1.32

7.86
3038.0
124.9
5452.5
1025.2
192.5
173.8
6594.4
6786.9
19590.0
0.05
3.52

0.28
949.1
60.0
2715.2
770.7
335.6
94.2
2092.5
2111.0
5772.1
0.02
1.15

c
A b B; A b C
A b B; A b C
A b B; A b C
A b B; A b C
AbC
A b B; A b C
AbCbB
AbCbB
AbCbB

Except conductivity (As cm 1 ) and pH.


Significance level (a = 0.05).
No statistically significant among sites.

contents. In general, BOD / COD ratio represented the


proportions of biodegradable organics in leachate.
Landfill leachate from a young landfill usually had a
higher BOD / COD ratio and leachate from an older or
stable one had a lower BOD / COD ratio. Generally

5000
Site A
Site B
Site C

COD (mg/L)

4000

3000

2000

1000

0
1/1/01

1/1/02

7/1/02

1/1/03

7/1/03

1/1/04

Date
500

400

SS (mg/L)

7/1/01

Site A
Site B
Site C

300

200

100

0
1/1/01

7/1/01

1/1/02

7/1/02

1/1/03

7/1/03

1/1/04

Date

Fig. 3. Variation of COD and SS contents at various landfills.

speaking, it is more suitable to use a biological treatment process when BOD / COD N 0.5 or COD /
TOC N 2.8 (Chain, 1977). The average ratios of
BOD / COD in landfills A, B, and C were 0.08,
0.06, and 0.05, respectively. This lower BOD / COD
value indicated that these landfills had reached a stable
status and probably were not suitable for biological
treatment processes which were the most commonly
used treatment methods in Taiwan. As a result, this
might be the reason that most of the landfills in
Taiwan have difficulty to fulfill the COD effluent
standards of 200 mg L 1. Consequently, it might be
necessary to include additional physical/chemical processes to achieve the desired removal efficiency. However, there were no statistically significant differences
of BOD / COD ratios among these sites.
The COD / TOC ratio of sites A, B and C were
about 2.99, 2.82, and 3.52, respectively. Although the
average value of site C was larger than both sites A
and B, the difference did not reach statistical significance level.
3.2.2. Correlations
Pearson correlation coefficients among the analyzed
chemicals are shown in Table 4. The landfill age was
negatively correlated with pH, COD, SS, VSS, TS,
color, TOC, BOD, conductivity, and SS. pH was correlative with landfill age, COD, TS, color, TOC, conductivity, and DS. SS was positively correlated with
COD, VSS, TS, color, TOC, conductivity and DS. The
COD content of the leachate samples was positively
correlated with pH, SS, VSS, TS, color, TOC, BOD,
conductivity, and DS. It was negatively correlated with

30

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

Table 3
Chemical properties of landfill leachatesa
1 a

Parameter (mg L

Age
pH
Conductivity
Salinity
COD
BOD5
Total solids
Suspended solid
Volatile solids
Fixed solids
Kjeldahl N
Ammoniacal N
Nitrate/nitrite N
Color (unit PtCo)
TOC
Total P
K
Na
Ca
Mg
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
a
b
c

Site A

Site B

Site C

JB, HKb

GDB, HKb

Kuwaitc

1016
7.038.50
3.5814.16

3201340
1297
18306120
4100
8370

40.1150

5802680
90439
0.293.75
198778
3201342
47.2137.5
27.8103
b0.15
0.010.18
0.014.38
0.265.44
0.185.27
0.040.14
b0.02
0.041.61

9
7.308.40
7.0540.68

4004340
26492
178014970
38332
51526

28303
2872
9.520.9
16209480
4471637
2.4315.9
1841799
2973524
67.2133.7
23163
b0.01
0.120.52
0.0011.48
0.2615.3
0.020.74
0.010.26
0.00050.09
0.0030.56

11
6.828.37
5.0029.60

8404210
16312
317010490
601750
72264

26.4219
180201
2.9626.7
158013875
3273992
4.815.14
3122243
4313142
15.961
15.7157
b0.01
0.041.26
0.020.9
0.3928
0.020.75
0.010.28
0.020.18
0.030.66

3.5
7.28.0
8.512.0
7.215.1
4891670

26805580

6851580
17704010
6751840
5941610
0.060.31

2.7214.1
270632
4841190

3563
b0.01
0.030.15
b0.05
1.143.25
0.050.24
0.070.18
0.030.12
0.242.55

11
7.28.4
2.511.8
4.09.5
1471590

9204500

4981580
3982923
1371060
65883
21.6179

0.363.78
78416
132743

926
b0.02
0.020.23
0.010.13
1.265.00
0.051.30
0.040.17
b0.10
0.130.39

6.98.2
5.16.9
5.78.1

157.99400 134018100 163063700


30600
13400 40045900

5.6122 254.12300
70290
5.2268
233410
100270

00.2
00.1
0.3554.1
4.21185
879

00.2
00.46

0.04.8
18.867

Except pH, age (year), conductivity (ms cm


Chu (1994).
Al-Yaqout and Hamodoa (2003).

5000

COD (mg/L)

4000

3000

2000
Site A
Site B
Site C

1000

100

200

300

400

Germanyc

), and salinity (ppt).

landfill age (correlation coefficient 0.57). The TS


content of the leachate was positively correlated with
pH, COD, SS, VSS, TS, color, TOC, BOD, conductivity, and DS as well. These relationships may provide a
useful means for estimating leachate strength and char-

USAc

500

BOD (mg/L)

Fig. 4. COD versus BOD for various landfill leachate.

600

acteristics on site, since some of the chemical parameters can be obtained easier than others.
3.2.3. Metals
Thirteen metals (Na, K, Ca, Mg, Fe, Cr, Ni, Mn, Pb,
Cd, Hg, Cu and Zn) in leachate were analyzed in this
research and listed in Table 5. In general, the concentrations of Na, K, Ca and Mg were the highest among these
13 metals in leachates. For example, the average sodium
concentrations of landfills A, B and C were about 783,
2028 and 1261 mg L 1, respectively. The closed landfill
A had the lowest concentration of Na, K, Fe, Cr and Ni
and the highest Mn contents among these three sites.
The mixed landfill B had the highest Na and Mg contents among these three sites which might be due to the
contents of bottom ash. Landfill C had the highest Fe
and Cr and the lowest Ca contents. As mentioned above,
it seemed that mixed landfill site B had the higher
contents of Na, Ca and Mg and the lower Fe and Cr
than active municipal landfill C had. Although there is
no violation to Taiwans effluent standards found in

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

31

Table 4
Pearson correlation coefficients of chemical contents
Landfill age
Landfill age
pH
COD
SS
VSS
TS
Color
TOC
BOD
Conductivity
DS

pH

1.00

0.19
1.00

COD

SS

0.57*
0.44*
1.00

0.28*
0.02
0.34*
1.00

VSS
0.43*
0.10
0.36*
0.66*
1.00

TS

Color

0.49*
0.42*
0.72*
0.29*
0.42*
1.00

0.57*
0.31*
0.79*
0.59*
0.46*
0.68*
1.00

TOC

BOD

0.49*
0.15
0.64*
0.36*
0.39*
0.43*
0.55*
1.00

Conductivity

0.44*
0.27**
0.76*
0.25
0.07
0.62*
0.58*
0.54*
1.00

0.60*
0.48*
0.78*
0.25**
0.39*
0.86*
0.71*
0.58*
0.64*
1.00

DS
0.48*
0.42*
0.71*
0.24**
0.41*
1.00
0.65*
0.43*
0.61*
0.86*
1.00

* Significance level 0.01.


** Significance level 0.05.

these three sites, the possible risk derived from heavy


metals in leachate should not be negligible. As stated by
Urase et al. (1997), even if the effluent from landfill sites
met the effluent standard, landfill leachate was still one
of the major sources of heavy metals discharged to the
surrounding environment.
The metal contents of leachates studied in this
research had been compared with landfills in Hong
Kong, Kuwait, USA and Germany as shown in Table
3. The leachate of USA had relatively higher contents
of Ca, Mg, Fe and Zn. In general, the leachates
generated from landfills in Taiwan (Table 3) had
higher K and Na than those of Hong Kong (JB and
GDB). Copper concentrations in Taiwans leachates
were higher than those of countries cited above
(Table 3). The higher contents of copper in leachates
should be monitored in the future to prevent contamination of soil and groundwater.

3.3. Effect of landfill age


The composition of leachate may be varied depending on the function of landfill age (Nanny and Ratasuk,
2002; Tatsi and Zouboulis, 2002). The relationship
between landfill ages and chemical contents of these
leachates are shown in Table 4. According to the Pearson coefficients analysis using SPSS (2000), the contents of COD, SS, VSS, TS, color, TOC, BOD and
conductivity were decreased as landfill age increased.
For example, the relationship of landfill age with COD,
BOD and SS is illustrated in Fig. 5. The COD, BOD
and SS contents were converged to lower concentrations when the landfill age increased. On the other
hand, the pH, BOD / COD, BOD/TOC and COD /
TOC did not appear to have a significant trend.
The property of leachate varied with landfill age
would be an important design factor to be considered,

Table 5
Metal concentrations of leachates at various landfills
Parameters (mg L

Na
K
Ca
Mg
Fe
Cr
Ni
Mn
Pb
Cd
Hg
Cu
Zn
a
b

Site A

Site B

Scheffes testb

Site C

Mean

SDa

Mean

SD

Mean

SD

782.65
455.42
98.71
49.76
1.74
0.07
0.09
1.46
0.01
0.02
0.01
0.26
0.36

318.29
174.98
48.25
19.18
1.30
0.04
0.03
1.25
0.01
0.05
0.01
0.86
0.40

2027.89
1158.93
87.84
77.39
5.15
0.28
0.16
0.40
0.02
b0.01
0.02
0.23
0.20

686.90
362.78
18.28
26.03
3.28
0.11
0.06
0.18
0.02

0.02
0.34
0.14

1261.28
924.24
56.66
53.56
8.24
0.73
0.18
0.36
0.03
b0.01
0.03
0.11
0.22

603.74
446.60
27.25
29.24
5.86
0.31
0.06
0.16
0.04

0.05
0.20
0.15

Standard deviation.
Significance level (a = 0.05).

AbCbB
A b B; A b C
C b A; C b B
A b B; C b B
AbBbC
AbBbC
A b B; A b C
B b A; C b A

32

H. Fan et al. / Science of the Total Environment 361 (2006) 2537


5000

Site A
Site B
Site C

4000

COD (mg/L)

increased with landfill age, but the Cu concentration


seemed to be decreased with time as shown in Fig. 6.
However, according to the results of Scheffes test,
there was no statistically significant difference of
metal contents between two active landfills. Therefore,
to continue monitoring metals in leachate might be
needed to ensure that the effluent metal contents were
under controls.

3000

2000

1000

3.4. Humic substance


0

10

12

14

16

600
500

Site A

BOD (mg/L)

Site B
Site C

400
300
200
100
0
4

10

12

14

16

Humic substances (humic acids (HA) and fulvic


acids (FA)) were the main organic components in
leachate. High concentration of humic substances
might increase the difficulty of treating the landfill
leachate (Calace and Petronio, 1997). For example,
humic substance might enhance the solubility of hydrophobic compounds through complexation. It could
modify bioavailability and biotoxicity of hazardous
compounds thereby impacting biodegradation or biouptake as well. This study extracted and analyzed HA,
FA and NHS (non-humic substance) from leachates.
The average contents of HA, FA and NHS in landfill

500

2
Site A
Site C

300

Cu (mg/l)

SS (mg/L)

Site A
Site B
Site C

Site B

400

200

100

0
4

10

12

14

16

Age (yr)

10

12

14

16

12

14

16

Age (Yr)

Fig. 5. Relationship between COD, BOD, SS, and landfill age.

2
Site A
Site B
Site C

Zn (mg/l)

the leachate treatment plant might have to be adjustable


to deal with different chemical contents as the time
went on. For example, Chuna Leachate Treatment
Plant (CLTP), Hsinchu, Taiwan, functioned properly
at the beginning of the landfilling while treating fresh
leachate. However, the treatment plant was unable to
handle the leachate to the desired level as the landfill
age increased. As a result, new treatment units are
planning to be added to the treatment systems to meet
the Taiwan EPA effluent standards.
The experimental results also indicated that the
heavy metal contents in landfills varied with time as
well. For example, the Zn concentrations seemed to be

10

Age (Yr)

Fig. 6. The variation of Cu and Zn contents in landfill leachates.

H. Fan et al. / Science of the Total Environment 361 (2006) 2537


Table 6
The concentration of HA, FA, and NHS in leachates
Site

Parameter

Mean
(mg L

HA
FA
NHS

B
%
1

94
100
142

28
30
42

Mean
(mg L

C
%
1

72
202
390

11
30
59

Mean
(mg L
101
123
257

%
1

)
21
26
53

leachates are shown in Table 6. The HA percentages of


landfills A, B and C were about 28%, 11%, and 21%,
respectively. Closed landfill A had higher percentage of
HA than active landfills B and C. These results were
slightly less than the ones reported in Artiola-Fortuny
and Fuller (1982) (60% HA) and Christensen et al.
(1998) (60% HA). The FA percentages of landfills A
and B were about 30%, and 26% for landfill C. These
values were higher than the contents reported in
Artiola-Fortuny and Fuller (1982) (10% FA). Active
landfills B and C had higher content of NHS than
that of closed landfill A. The HA / FA ratios of A, B
and C were about 0.94, 0.36 and 0.82, respectively. The
lower HA / FA ratio of site B might be due to that of the
mixed landfill of MSW and bottom ashes had lower
organic contents in solid wastes.
3.5. Elemental and FTIR analysis
Organic contents of leachates were further characterized using elemental analysis and FTIR. The results
of C, H, O, N, and S in three landfill leachates A, B and

33

C and commercial humic acids (Fisher co.) are shown


in Table 7 along with results reported in literature
(Nanny and Ratasuk, 2002; Kang et al., 2002). The
percentages of carbon in central Taiwans leachates
were significantly lower than those reported by
Nanny and Ratasuk (2002) and Kang et al. (2002).
The results indicated that the characteristics of leachates
generated from central Taiwan were very different from
other countries. The carbon contents in central Taiwan
leachates were significantly less than that of commercial humic acids (Fisher Scientific Co.) as well. In
addition, closed landfill A had lower C% and higher
N% than those of active landfills B and C. The atomic
ratios of H / C, O / C and N / C were calculated from the
element analysis results as shown in Table 7. If the
molar H / C ratio is clustered around 1.0, it implied a
chemical structure consisting predominantly of aromatic framework (Kang et al., 2002). The molar H / C ratios
of landfill leachates A, B and C were about 4.35, 2.25
and 1.77, respectively. The H / C ratio of landfill C was
similar to those landfills in Hong Kong and USA
(Nanny and Ratasuk, 2002; Kang et al., 2002). Usually,
a lower H / C value indicated a higher aromatic framework. Therefore, the aromaticity of the closed landfill
leachate A was lower than those of active landfills B
and C and the mixed landfill B had lower aromaticity
than direct landfill leachate C had. The relatively high
H / C ratios in the landfill A implied that the structures
contained significant portions of aliphatic functional
groups. The O / C ratios of landfills A, B and C were
about 4.32, 1.82 and 1.58, respectively. The higher

Table 7
Elemental composition (normalized to 100% of organic components) and ratios of leachate (molar ratio)
Sample

C%

H%

O%

N%

S%

H / Ca

O / Ca

N / Ca

Site A
Site B
Site C
Fisher sci.b
Landfill Gc
Landfill Pc
Landfill Nc
Aquatice
Terrestriale
NLFg
SELAg
EOg

11.44
24.33
28.47
46.09
56.2
57.1
56.1
5360
5462
60.48
61.73
63.09

4.15
4.57
4.21
5.55
8.8
7
7.2
3.75.1
2.95.8
6.97
7.44
7.35

65.94
59.15
59.88
46.13
26.7
30.2
29.3
33.440.8
29.536.8
28.11
25.89
26.27

15.3
9.96
6.05
0.78
8.3
5.7
7.4
2.02.1
1.64.8
2.32
3.71
1.79

3.17
1.99
1.38
1.45
NDd
ND
ND
f

4.35
2.25
1.77
1.44
1.54
1.48
1.88
0.741.15
0.561.29
1.37
1.44
1.39

4.32
1.82
1.58
0.75
0.39
0.4
0.36
0.420.58
0.360.51
0.35
0.31
0.31

1.15
0.35
0.18
0.01
0.11
0.09
0.13
0.0290.034
0.0220.076
0.03
0.05
0.02

a
b
c
d
e
f
g

Molar ratio.
Humic acid obtains from Fisher Scientific Co.
Landfills in Korea(Kang et al., 2002).
ND= Not detected.
Typical values of Aquatic and Terrestrial humic acids.
Data not available.
Landfills in Oklahoma, USA; NSF, Norman Landfill; SELA, Southeast Landfill Authority; EO, East Oak (Nanny and Ratasuk, 2002).

34

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

Table 8
Absorption coefficients of leachates
Parameter

Site A

Site B

Site C

e 280 (280 nm)


e 465 (465 nm)
e 665 (665 nm)
e 465 / e 665

1.63
0.11
0.01
11

2.27
1.18
0.21
6

2.26
1.41
0.28
5

dicted with the results reported by Kang et al. (2002).


The authors reported that aromatic components and
molecular size were increased with landfilling age.
However, it was not the case in this research. It might
be due to the different types of MSW that were disposed in these landfills.
FTIR spectra of leachates are illustrated in Fig. 7.
The FTIR spectra of the leachates offered information
about specific molecular structures and various functional groups. For example, 34003200 cm 1 due to
intermolecular OH stretching or H-bounded OH, 2980
and 2850 cm 1 due to asymmetrical and symmetrical
stretching, respectively, of methyl and methylene CH
bond, 2900 cm 1 due to aliphatic CH stretching, 1720
cm 1 related to CjO stretching in carboxylic acids,
aldehydes and ketone groups, 16901710 cm 1 due to
CjO stretching of COOH and ketonic CjO, a shoulder at 1650 cm 1 due to stretching of CjC bonds
present in aromatic or asymmetric alkenes conjugated
with CjO or carboxylate, 1540 cm 1 (CjN stretching, amide II band), 1240 cm 1 (CO stretching)
(Christensen et al., 1998; Nanny and Ratasuk, 2002;
Kang et al., 2002).
As indicated in Fig. 7, the content of aliphatic
groups (2900 cm 1) appeared to be more pronounced
in the active landfills sites B and C than closed landfill
A. The spectral features of leachate indicated that the
aromatic character of the leachate was in the order of
C N B N A. This result was in agreement with humic
substance (HA and FA) and elemental analysis. The
spectral features of leachate also indicated that the
aromatic character in the leachates was relatively

O / C ratio of leachate A indicated that it had higher


contents of oxygen-possessing carbohydrate than activate landfills. The O / C ratios in Taiwans leachate were
relatively higher than those found in literatures indicated in Table 7. Similar trends of N / C ratios were
obtained as well. That is, site A had a significant higher
N / C ratio than other landfills.
Adsorption coefficient at 280 nm (e 280) and ratio of
absorption coefficients at 465 and 665 nm (e 465/e 665)
were measured in this research as well (Table 8). The
value of e 280 was used as an indicator for the aromaticity of a sample structure. The e 280 for A, B and C was
about 1.63, 2.28 and 2.26 m, respectively. Since the
landfill A had lower adsorption at 280 nm, this meant
that the aromaticity of the leachate A was lower than
those of B and C. This result was in agreement with
previous findings according to the H / C values showed
in Table 7. In this study, the values of e 465 / e 665 were
generally known to be inversely proportional to molecular weight (Kang et al., 2002; Chin et al., 1994). The
values of e 465 / e 665 for landfills A, B and C were about
11, 6, and 5, respectively. This indicated that the molecular weight of the leachate A is lower than those of
active landfills B and C. However, this result contra12

Site A
Site B
Site C
Humic acids (Fisher Sci.)

10

Kulelka Munk

1000

2000

Wave number (cm-1)

Fig. 7. FTIR spectra of leachates.

3000

4000

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

35

leachates in SS, VSS, color, TOC, and BOD contents.


Winters leachate had higher pH, COD, TS and conductivity than those of summer. Spring and winter had
higher TS and DS than both summer and fall.
There was no statistical seasonal effect for landfill
leachate of B in pH, COD, color, TOC, BOD and
conductivity. SS of landfill B in fall was higher than
that of winter. VSS contents were highest in fall among
four seasons. TS and DS in spring were higher than that
of summer. It was interesting to point out that there was
no significant seasonal difference of chemical compositions in site C. As cited in pervious sections, rainfall
was an important factor affecting the characteristics of
leachates (Chen, 1996). In this study, not all chemical
compositions in leachate were significantly influenced
by rainfall.

lower than that of commercial humic acid indicated in


Fig. 7.
3.6. Seasonal effect
Seasonal effect of landfill leachates was investigated
in this research as well. In general, spring and summer
are considered raining seasons and fall and winter are
dry seasons in Taiwan. Rainfall is an important factor
for leachate, for example, Linde et al. (1995) indicated
that 15%~50% of rainfall had turned leachate. Parameters investigated in seasonal effect included pH,
COD, SS, VSS, TS, DS, color, TOC, BOD and conductivity and seasonal statistical significance for various landfill leachates are listed in Table 9. For closed
landfill A, there was no significance seasonal effect of

Table 9
Seasonal effect of leachates
Site

Parameter

Season

Mean (mg L

pH

Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter
Spring
Summer
Fall
Winter

7.8
7.4
7.8
8.0
764
444
592
956
4884
2664
3194
4856
9285
5935
8564
10776
4848
2634
3161
4820
136
148
242
128
82
135
331
138
11843
7627
8510
10434
11707
7479
8268
10306

COD

TS

Conductivity

DS

SS

VSS

TS

DS

SD.

Min

Max

Scheffes testb

0.4
0.3
0.2
0.4
369
247
96
258
1327
781
425
657
3264
1790
1615
1973
1315
786
423
649
49
78
81
30
19
83
115
51
1838
3070
1067
828
1833
3047
1139
831

7.1
7.0
7.6
7.6
310
160
510
509
2480
1830
2600
3960
5670
3580
5800
8220
2463
1791
2578
3946
72
38
153
68
58
52
228
80
9710
1780
7610
9370
9608
1742
7361
9226

8.2
7.8
8.1
8.5
1340
900
720
1258
6120
4030
3620
5700
14160
9390
9600
13030
6100
4026
3589
5650
190
283
332
160
104
261
526
224
14970
11180
9860
11975
14899
11055
9693
11855

Winter N Summer

Winter N Summer

Spring N Summer, Fall


Winter N Summer, Fall
Winter N Summer

Spring N Summer, Fall


Winter N Summer, Fall
Fall N Winter

Fall N Spring, Summer, Winter

Spring N Summer

Spring N Summer

36

H. Fan et al. / Science of the Total Environment 361 (2006) 2537

Table 10
Toxicity of leachates at various landfills
Landfill

Range (EC50)a

Classb

A
B
C

N100
N100
3.019

Non-toxic
Non-toxic
Confirmed toxicitySevere toxic

Sampling periods: Feb. 2001Jul. 2003.


b
EC50 N 100, non-toxic; 100 N EC50 N 40, potential toxicity;
40 N EC50 N 10, confirmed toxicity, and EC50 b 9 severe toxicity
(1999).

3.7. Toxicity
Chemical analysis of environmental samples provides a measurement for the total concentration of
potentially harmful substance. However, chemical techniques may also be unable to detect certain bunknownQ
compounds. Assessment of potential environmental
risk of contaminated groundwater cannot be evaluated
by chemical means alone (Boyd et al., 1997). Therefore, microtox acute tests were applied in this research
to evaluate the toxicity of the leachate. Microtox acute
tests had the advantages of simple, fast and sensitive.
The test used the luminescent bacteria (Vibrio fischeri)
as a toxicity indicator. The metabolic process and light
production of bacteria were both intrinsically linked
respiration via the use of NADH and oxygen. Therefore, the end product of the luminescent bacteria also
included an appreciable quantity of light. Anything that
will effect the respiration of the luminescent bacterium
would cause a corresponding response in light level.
The sample was toxic if it caused a decrement in light
compared to the control. Therefore, the light could be
measured to determine changes in light level caused by
a toxic response (Boyd et al., 1997).
The results of microtox acute tests are shown in
Table 10. The EC50 (15 min) for landfills A, B and C
were 0.5, N 100, and 0.1, respectively. EC50 (15 min)
indicated the toxicant concentration caused the lamination of bacteria to reduce 50% at a 15-min reaction
time. In general, the EC 50 can be classified as follows:
(1) EC50 N 100, non-toxic. (2) 100 N EC50 N 40, potential
toxicity (3) 40 N EC50 N 10, confirmed toxicity, and (4)
EC50 b 9 severe toxicity (Marsalek et al., 1999). As in
Table 10, the toxicity of sites A and B was not significant, however the toxicity of site C was highly toxic.
This result might indicate that the mixed landfilling was
helpful on reducing the toxicity of leachate. In Taiwan,
there are more than 75 simple landfills without proper
lining systems. Most of these simple landfills were
located in remote mountain areas and some of them
were located in water resource preservation area. There-

fore, it should be concerned that the leachates might


cause contamination of the soil and groundwater.
4. Conclusions
In Taiwan, due to the increasing percentage of MSW
disposed in the landfills, the compositions of leachate
were modified as well. To better understand the different types of leachate generated in Taiwan, three typical
landfills, namely closed landfill A, mixed landfill B and
direct landfill C, in central Taiwan were investigated in
this research. These results indicated that the landfill
age was negatively correlated with pH, COD, SS, VSS,
TS, color, TOC, BOD, conductivity, and SS. On the
other hand, the pH, BOD / COD, BOD / TOC and COD /
TOC did not appear to have significant correlation with
landfill age. The organic contents of leachate in closed
landfill A were significantly less than active landfills B
and C as predicted, but the leachate generated from
mixed landfill B did not significantly reduce the organic
contents when compared with landfill C. However, the
mixed landfill site B had higher contents of DS, TS,
conductivity, Na, Ca and Mg and lower Fe and Cr than
active municipal landfill C. This might be due to the
contents of bottom ash in landfill B. Landfill C had the
highest Fe and Cr and the lowest Ca contents.
Closed landfill A had higher percentage of HA than
active landfills B and C. An older landfill had higher
percentage of humic substances (HA and FA). The aromaticity of the closed landfill (leachate A) was lower than
that of active landfills B and C. In addition, the mixed
landfill B had lower aromaticity than direct landfill leachate C. Leachate A contained the significant portions of
aliphatic functional groups and higher contents of oxygen-possessing carbohydrate than those of activate landfills. One potential advantage of mixed landfill was that it
might help to reduce the toxicity of leachate.
Acknowledgements
The authors would like to thank the National Science
Council of Taiwan and Hungkuang University for financially supporting this research. We also thank Mr.
Chinnan Ke of NTHU Instrument Center at Hsinchu
National Tsing Hua University for his help with the
heavy metal analyses (ICP AES).
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